Tichifunga nezvekunetseka kwezvakatipoteredza uye shanduko yesimba, electrochemical CO2 kuderedzwa (ECR) kune yakakosha-akawedzera multicarbon (C2+) mafuta uye makemikari, achishandisa magetsi anovandudzwa, inopa yakanakisa mhinduro yenguva refu yekuvhara iyo kabhoni kutenderera neakawedzera mabhenefiti ehupfumi zvakare.Nekudaro, electrocatalytic C─C kubatanidza mune aqueous electrolytes ichiri dambudziko rakavhurika nekuda kwekuderera kusarudza, kuita, uye kugadzikana.Dhizaini yezvinokonzeresa uye mareactor inobata kiyi yekugadzirisa iwo matambudziko.Isu tinopfupikisa kufambira mberi kwazvino mukuita kwakanyatsoita C─C kubatana kuburikidza neECR, nekusimbisa pamaitiro emagetsi emagetsi uye electrocatalytic electrode / reactor dhizaini, uye maitiro avo anoenderana.Mukuwedzera, mabhodhoro azvino uye mikana yeramangwana yeC2 + chigadzirwa chizvarwa inokurukurwa.Isu tinovavarira kupa ongororo yakadzama yeiyo-ye-iyo-inoyevedza C─C nzira dzekubatanidza kunharaunda kuti iwedzere kusimudzira uye kurudziro mukunzwisisa kwakakosha uye tekinoroji mashandisiro.

Kuburitswa kwakanyanya kwecarbon dioxide (CO2) mumhepo kwakonzera mhedzisiro yezvakatipoteredza uye kunopa njodzi yekukurumidzira uye isinga gadzirise nharaunda dzevanhu (1, 2).Sezvo CO2 yemhepo yakawedzera zvakanyanya kubva pa270 ppm (zvikamu pamiriyoni) mukutanga 1800s kusvika 401.3 ppm muna Chikunguru 2015, kubvumirana kwepasirese pakudzokorodza kabhoni tsoka inoburitswa nezviitiko zvevanhu kwasvikwa (3, 4).Kuona iyo yepedyo loop yekabhoni tsoka, imwe nzira ingangove yekuchinjisa kutsamira kweazvino simba uye maindasitiri emakemikari kure kubva kumafuta ezvicherwa kuenda kunowanikwazve solar nemhepo (5-8).Nekudaro, chikamu chesimba kubva kune izvo zvinogonekazve masosi chinongogumira ku30% nekuda kwechimiro chavo chepakati, kunze kwekunge nzira dzekuchengetedza simba dzakakura dzivepo (9).Saka, seimwe nzira, kutorwa kwe CO2 kubva kunzvimbo dzakadai semagetsi emagetsi, inoteverwa nekushandurwa kuita makemikari feedstocks uye mafuta, inonyanya kushanda (9-12).Electrocatalytic CO2 kuderedza (ECR) kushandisa magetsi anovandudzwa inomiririra mhinduro yenguva refu nekuda kwemamiriro ekushanda akapfava anodiwa pakushandurwa, umo zvigadzirwa-zvakawedzerwa-zvakawedzerwa zvinogona kugadzirwa zvakasarudzwa (13).Sezvinoratidzwa mumufananidzo 1, mune iyi nzira, electrochemical electrolyzer inoshandura CO2 nemvura mumakemikari nemafuta anoshandiswa nemagetsi anogona kuvandudzwa.Iyo mafuta inoguma inokwanisa kuchengetedza kwenguva refu uye inogonawo kugoverwa kana kupedzwa, ichipa CO2 semarara makuru, iyo ichatorwa uye inodyiswa zvakare kune reactor kuvhara loop.Zvakare, izvo zvinokonzeresa diki-morekuru kemikari feedstocks [semuenzaniso, kabhoni monoxide (CO) uye formate] kubva kuECR inogona kushandiswa seyakagadzirwa zvinhu kune zvakanyanya kuoma makemikari synthesis.

Mafuta nemakemikari anogona kuwanikwa kubva kuECR neakavharwa kabhoni cycle inofambiswa neinovandudzwa simba masosi sesolar, mhepo, uye hydro.Cell engineering uye catalyst engineering inotamba mabasa akakosha kusimudzira kusarudza, kuita, uye kugona kwe CO2 shanduko kuita kukosha-yakawedzerwa C2+ zvigadzirwa zvine yakakwira simba density.

Zvisinei, CO2 inonyatso kugadzikana mutsara molecule ine yakasimba C═O bond (750 kJ mol-1) (14), zvichiita kuti zviome kutendeuka kwe electrochemical.Nokudaro, inoda chikwata chepamusoro chekugadzirisa, icho, icho, chinotungamira kune zvakakosha kudarika (15).Uyezve, ECR mune aqueous electrolyte inosanganisira akawanda-elektroni / proton ekufambisa maitiro pamwe chete nenhamba dzakasiyana-siyana dzinogona kuitika dzepakati uye zvigadzirwa (16-18), zvichiita kuti zviome zvakanyanya.Tafura 1 inopfupikisa hafu ye electrochemical thermodynamic reactions yezvakanyanya ECR zvigadzirwa, zvinosanganisira CO, methane (CH4), methanol (CH3OH), formic acid (HCOOH), ethylene (C2H4), ethanol (CH3CH2OH), zvichingodaro, pamwe chete ne inoenderana neyakajairwa redox mikana (19).Kazhinji, panguva yeECR maitiro, CO2 mamorekuru anotanga adsorption uye kudyidzana nemaatomu panzvimbo inokonzeresa kuumba *CO2-, ichiteverwa nekasiyana nhanho kuendesa mapurotoni uye/kana maerekitironi kune akasiyana ekupedzisira zvigadzirwa.Semuyenzaniso, CH4 inofungidzirwa kuti inoumbwa nenzira dzinotevera: CO2 → *COOH → *CO → *CHO → *CH2O → *CH3O → CH4 + *O → CH4 + *OH → CH4 + H2O (20).

Mufananidzo 2A inopfupisa kubudirira kweFaradaic (FE) pasi pemitengo yakasiyana-siyana yekugadzirwa (ikozvino density) kune yakashumwa ECR electrocatalysts, iyo inomiririra chigadzirwa chekusarudza kwekuita (21-43).Zvinonyanya kukosha, nepo iyo-ye-iyo-iyo-yemagetsi maelectrocatalysts anogona kushandura CO2 kuita C1 zvigadzirwa (CO kana formate) ine inopfuura 95% FE pasi pehuwandu hwekugadzirwa kwepamusoro (> 20 mA cm−2 yeH-mhando sero uye> 100 mA cm- 2 yekuyerera sero) (9, 21, 22, 25, 28, 44, 45), iyo inonyanya kusarudzwa (> 90%) uye kugadzirwa kwakanaka kweakawanda anowanikwa multicarbon (C2 +) makemikari haasati aitika kusvika zvino.Izvi zvinokonzerwa nekuti kubatanidza kune C2+ zvigadzirwa zvinoda kusvika uye adsorption akati wandei CO2 mamorekuru kumusoro, nhanho shanduko, uye nzvimbo yekumisikidza (13).Kuti zvive zvakananga, sezvinoratidzwa mumufananidzo 2B, maitiro anotevera e * CO intermediates anosarudza yekupedzisira C2 + zvigadzirwa zve ECR.Kazhinji, C2H6 uye CH3COO− vanogovana zvakafanana *CH2 yepakati, iyo inogadzirwa kubva kune proton-yakabatana electron ekufambisa matanho e *CO.Imwezve protonation ye * CH2 inopa * CH3 yepakati, iyo inotungamirira pakuumbwa kweC2H6 kuburikidza ne * CH3 dimerization.Kusiyana nechizvarwa cheC2H6, CH3COO− inoumbwa neCO kuiswa mu *CH2.Iyo * CO dimerization ndiyo nhanho-yekutarisa nhanho yeC2H4, CH3CH2OH, uye n-propanol (n-C3H7OH) kuumbwa.Mushure menhevedzano yekufambisa maerekitironi uye nhanho dzeprotonation, iyo * CO─CO dimer inoumba * CH2CHO yepakati, iyo inoshanda sedanho rekusarudza-kusarudza kweC2H4 uye C2H5OH.Mukuwedzera, zvakaonekwa kuti kuderedza * CH2CHO kusvika kuC2H4 ine simba rekudzivirira simba rakaderera pane kushandura * CH3CHO kusvika kuC2H5OH (46), iyo inogona kutsanangura FE yakakwirira yeC2H4 pamusoro peC2H5OH pane zvakawanda zvinogadzirisa mhangura.Uyezve, yakagadzikana yeC2 yepakati inogona kuendesa kune n-C3H7OH kuburikidza neCO kuiswa.Iyo yakaoma uye isingadzoreki maitiro ekuita nzira panguva yeC2 + kuumbwa kwemakemikari inonyanya kukonzerwa nekuwanda kwakawanda kubvumidza kune nzvimbo dzeprotonation, pamwe nekugona kubatanidzwa kwenonelectrochemical nhanho (19, 47).Saka nekudaro, dhizaini yema electrocatalyst akasarudzika chinhu chinodiwa kune chaiyo C2 + chigadzirwa kuumbwa pagoho repamusoro.Muongororo iyi, isu tinovavarira kuratidza kufambira mberi kwazvino pamaitiro e electrocatalyst dhizaini yekusarudza C2 + chigadzirwa chizvarwa kuburikidza neECR.Isu tinopawo pfupiso yekunzwisisa kwemaitiro ane hukama.Electrode uye reactor dhizaini ichasimbiswa zvakare kuratidza maitiro ekubudirira, yakagadzikana, uye yakakura-chiyero kushanda kweECR.Uyezve, tichakurukura matambudziko akasara uye mikana yeramangwana yekushandurwa kwe electrochemical ye CO2 kuva yakakosha-yakawedzerwa C2 + makemikari.

(A) The FE pasi pemhando dzakasiyana dzekugadzirwa (ikozvino density) kune yakashuma ECR electrocatalysts (21-43, 130).(B) Yakawanda inogoneka C2 + nzira panguva yeECR.Yakadhindwa nemvumo kubva kuAmerican Chemical Society (47).

Electrocatalytic shanduko ye CO2 kuita makemikari mafuta uye feedstocks inogona kuve tekinoroji yekuwana kabhoni-neutral simba kutenderera (11).Zvisinei, iyo FE yeC2 + zvigadzirwa ichiri kure nekushanda kwekushanda, apo hurumende-ye-the-art catalysts inobvumira kugadzirwa kweC2 zvigadzirwa neine 60% FE (13, 33), nepo C3 kugadzirwa kunogumira pasi pe10% FE (48, 49).Reductive coupling ye CO2 kune C2 + zvigadzirwa zvinoda heterogeneous catalysts ine yakanyatso kurongeka morphological uye zvemagetsi zvivakwa (50, 51).Iyo inokonzeresa nzvimbo inoda kuputsa hukama hwekuyera pakati pevapakati (47, 52, 53).Zvakare, kuti uwane C─C chisungo chekugadzira, iyo yakanyudzwa maitiro epakati pane inokonzeresa nzvimbo inofanirwa kunge iri padhuze kune mumwe nemumwe.Uyezve, nzira kubva kune yekutanga adsorbed yepakati yakananga kune chaiyo C2+ chigadzirwa inoda kudzorwa zvakanaka nekuda kweakawanda proton-anobatsira maelectron ekufambisa matanho.Tichifunga nezvekuoma kwepamusoro kwe CO2 kuderedza kune C2 + zvigadzirwa, electrocatalysts inofanira kunyatsogadziriswa kuti iwedzere kusarudzwa.Zvinoenderana nemhando dzepakati uye maumbirwo emakemikari, tinoisa zvigadzirwa zveC2+ kuita multicarbon hydrocarbons uye oxygenates (4, 54).Kuti uswedere ma electrocatalysts anonyatso shanda kune chaiyo C2+ molecule kugadzirwa, akati wandei anokonzeresa dhizaini, senge heteroatom doping, crystal facet regulation, alloy/dealloying, oxidation state tuning, uye surface ligand control, zvakaratidzwa (35, 41, 55-61) .Yakakwana dhizaini inofanirwa kufunga zvine musoro mhedzisiro yataurwa uye kuwedzera mabhenefiti.Zvikasadaro, kunzwisisa izvo zvinoshanda-saiti motifs zvinotungamira kune yakadaro yakasarudzika hunhu inogona kuwedzera kupenya mwenje pane chaiyo catalyst dhizaini yeC─C coupling.Nekudaro, magadzirirwo eECR catalyst akananga kune chaiwo zvigadzirwa (multicarbon hydrocarbons uye oxygenates) uye yakabatana michina ichakurukurwa muchikamu chino.

C2+ mahydrocarbons, akadai seC2H4, makemikari anexus emhando dzakasiyana dzemakemikari maindasitiri, akadai sekugadzirwa kwepolyethylene (62, 63).Kunze kwezvo, inogona kushandiswa zvakananga sehuni yewelding kana musanganiswa wechikamu mugasi rechisikigo (12).Hydrogenation yeCO (Fischer-Tropsch synthesis) uye CO2 yakashandiswa kugadzira C2 + hydrocarbons kwenguva yakareba muchiyero cheindasitiri asi ichipikiswa nekushandiswa kwesimba kwakanyanya uye kukanganisa kwezvakatipoteredza (64).Mukusiyana kwakasiyana, electrochemical CO2 kuderedzwa uchishandisa simba rinogona kudzokororwa rinopa nzira yakachena uye yakasimba.Kuedza kukuru kwakaitwa kugadzira maelectrocatalyst anoshanda akananga kuC2+ hydrocarbons (32, 33, 65–70).

Bimetallic electrocatalysts yakave yakaongororwa zvakanyanya kuti iparadze hukama hwekuyera panguva yekushandura kwe electrochemical CO2, iyo inogona kudzikamisa kiyi yepakati uye kuderedza kuwanda kwepamusoro uye, nokudaro, kuwedzera kusarudzwa (71-74).Nepo nhevedzano yezvigadzirwa zvealloy zvinosanganisira Au-Cu, Ag-Cu, Au-Pd, uye Cu-Pt zvakaratidzwa zvehunyanzvi hwekugadzira C1 nekudzikamisa iyo yakakosha yepakati (73, 75), iyo alloy mhedzisiro yakanangana neC2 + hydrocarbon kuumbwa kunoratidzika. kuva yakaoma kunzwisisa (76).Semuenzaniso, muCu-Ag bimetallic system, kugoverwa kwechigadzirwa kunogona kudzorwa zviri nyore nekugadzirisa chiyero cheatomu yeAg neCu (77).Iyo yepamusoro Cu-rich sampu inosarudzwa kugadzirwa kwehydrocarbon, nepo zvigadzirwa zvepamusoro Ag-rich imwe inotongwa neCO, ichiratidza kukosha kweatomu reshiyo kune alloyed ECR electrocatalysts.Mhedzisiro yejometri inokonzerwa neatomu yemunharaunda inogona kukanganisa zvakanyanya kusimba kwekusunga kwepakati.Gewirth uye vashandi pamwe chete (36) vakaratidza kuti Cu-Ag alloys kubva kune-additive-controlled controlled electrodeposition yakaratidza ~ 60% FE yeC2H4 mune alkaline flow electrolyzer (Fig. 3, A uye B).Muchiitiko ichi, yakagadziridzwa C2H4 sarudzo inogona kuwanikwa ne morphology uye Ag-kurodha tuning.Nzvimbo dzeAg dzaitendwa kuita basa rekusimudzira CO kuumbwa panguva yeECR.Zvadaro, kuwanikwa kwakakwana kweCO yepakati kunogona kubatsira C─C kubatanidza muCu yakavakidzana.Kunze kwezvo, Ag inogonawo kukurudzira kuumbwa kweCu2O panguva yeCu-Ag catalyst synthesis (Fig. 3C), zvichiita kuti C2H4 iwedzere kushanda zvakanaka.Iyi synergy inovhura mikana mitsva yekugadzira C─C yekubatanidza catalysts.Uyezve, iyo yekusanganisa patani yesimbi dzakasiyana mualloy system inogona zvakare kuona kugoverwa kwezvigadzirwa zveECR.Kushandisa Pd-Cu alloy semuenzaniso (Fig. 3D), Kenis uye vashandi pamwe chete (71) vakaratidza kuti chikamu-chakaparadzaniswa chePd-Cu catalyst chinogona kupa sarudzo yepamusoro (~ 50%) yeC2H4 kana ichienzaniswa neyakarongerwa uye yakakanganiswa. vamwe.Zvinoenderana neiyo d-bhendi dzidziso, kazhinji, shanduko yesimbi ine yakaderera d-bhendi nzvimbo inoratidza isina kusimba yekusunga kweiyo in situ inogadzirwa yepakati panzvimbo yesimbi (78).Nepo chikamu-chakapatsanurwa Pd-Cu alloy yakaratidza zvakafanana catalytic selectivity uye chiitiko cheCO neCu nanoparticles (NPs), yakapa akasiyana zvachose anosunga simba kune vepakati nePd tuning.Sezvinoratidzwa mumufananidzo 3E, chikamu-chakaparadzaniswa neCu-Pd alloy yakaratidza yakaderera-yakarara d-band centre, asi iyo yeCu NP ndiyo yakakwirira.Inoratidza kuti chikamu-chakaparadzaniswa neCu-Pd alloy yakanga ine simba rakaderera rekusunga reCO yepakati.Izvi zvinoreva kuti geometric uye maitiro ekugadzirisa anogona kuita basa guru kudarika magetsi ekugadzirisa hydrocarbon selectivity muchikamu-chakaparadzaniswa neCu-Pd alloy case.Kusvika iye zvino, chete mhangura yakachena kana mhangura-based alloy inoratidza hukuru hwekusarudza uye basa re electrochemical kuderedza CO2 kusvika kuC2 + hydrocarbons.Nekudaro, zvinonyanya kukosha kugadzira inoveli electrocatalyst yeC2 + hydrocarbon kugadzirwa kubva kuECR.Yakafuridzirwa ne CO2 hydrogenation, chidzidzo chekutanga chakaratidza kuti Ni-Ga alloy ine zvikamu zvakasiyana inogona kushandiswa kuC2H4 chizvarwa (79).Yakaratidza kuti Ni5Ga3 firimu inogona kuderedza CO2 kuC2H4 uye ethane (C2H6).Kunyangwe iyo FE yakananga kuC2+ mahydrocarbons iri pasi pe5%, inogona kuvhura mitsetse mitsva yekuongorora kwe electrocatalyst yakananga kuC─C coupling zvichibva pane alloy maitiro.

(A kusvika C) Cu-Ag bimetallic catalysts yakagadzirwa ne-additive-controlled electrodeposition: (A) scanning electron microscopy (SEM) yeCu wire, Cu-Ag poly, uye Cu-Ag waya uye (B) inoenderana neC2H4 FE.(C) EXAFS yakaratidza kuti Cu-Ag waya yaive yakasanganiswa uye Cu(I) oxide yakaratidzwa.(A) kusvika (C) anogadzirwazve nemvumo kubva kuAmerican Chemical Society (36).(D uye E) Cu-Pd zvinokonzeresa zvine maitiro akasiyana ekusanganisa: (D) Mufananidzo, kutapurirana electron microscopy (TEM) mifananidzo, uye simba-inoparadzira spectroscopy element mepu yeakarongedzerwa, akaomeswa, uye chikamu-akapatsanurwa Cu-Pd alloys uye (E. ) pamusoro valence bhendi photoemission spectra uye d-bhendi centre (yakatwasuka mutsara) yeCu-Pd alloys maererano neFermi level.(D) uye (E) anogadzirwazve nemvumo kubva kuAmerican Chemical Society (71).kana, mayunitsi asina kurongeka.

Kunze kweiyo alloy mhedzisiro, manipulating iyo oxidation nyika imwe huru musimboti wekugadzirisa mashandiro emagetsi emagetsi, ayo anogona kukanganisa magadzirirwo emagetsi enzvimbo.Muenzaniso wekutanga weiyo oxidation state tuning ye catalyst ndeye kushandisa oxide-yakatorwa zvinhu.Iyo yakasara yemhando yeokisijeni iri pamusoro kana pasi peiyo catalyst mushure me in situ kuderedza inogona kudzora oxidation mamiriro enzvimbo yesimbi.Semuenzaniso, plasma-oxidized Cu yakaratidza kupfuura 60% selectivity yakananga kuC2H4, iyo yakanyorwa kune kuderedza-resistant Cu + (37).Kuti tisimbise kuti Cu + ndiyo inokosha parameter ye high ethylene selectivity, takaita maitiro ekutonga tichishandisa plasma yakasiyana (Fig. 4A).In situ hard x-ray absorption spectroscopy yakaratidza zvakare kuti maokisidi akasara mu (sub) pamusoro pedenga akagadzikana pamamiriro ekuderedza, ane huwandu hunokosha hweCu+ marudzi asara mushure meawa 1 yekuderedza pane zvingangove zvakakwirira zve -1.2 V zvichienderana nekudzoka shure. hydrogen electrode (RHE).Uyezve, electroredeposition yemhangura kubva kune sol-gel yemhangura oxychloride yakasimbiswa zvakare kuti yakagadzikana pamusoro peCu + marudzi anogona kuvandudza kusarudzwa kweC2H4 (61).Iyo oxidation mamiriro emhangura inokonzeresa pasi peakasiyana akashandiswa anogona kuteverwa uchishandisa nguva-yakagadziriswa in situ yakapfava x-ray absorption spectroscopy.Nhanho yekutanga yekushandura kubva kuCu2+ kuenda kuCu+ inokurumidza kwazvo;zvisinei, kuwedzera kwe electrochemical kuderedzwa kweCu + marudzi kuCu0 kunononoka zvikuru.Inenge 23% yeCu + marudzi anoramba aripo kunyange mushure meawa 1 nguva dzose kuderedza pasi -1.2 V kurwisana neRHE (Fig. 4B).Zvidzidzo zveMechanistic zvakaratidza kuti kusangana pakati peCu+ neCu0 kunotungamira mukukwezva kwemagetsi pakati pepakati sezvo C atomu ye *CO @ Cu+ ichichajwa zvakanaka, nepo iyo ye *CO @ Cu0 ichichajwa zvisina kunaka (80), iyo inosimudzirawo C─C bond kuumbwa uye nekudaro inogadzira C2+ hydrocarbons.Pamusoro pezvinhu zvakatorwa neoxyde, copper nitride (Cu3N) yakashandiswawo kuwana (sub) pamusoro peCu+ marudzi kuderedza dimerization simba barriers ye * CO (81).Mukuwedzera, zvichienzaniswa ne-oxide-derived Cu, Cu3N-derived Cu + marudzi akatonyanya kugadzikana (Fig. 4C).Somugumisiro, iyo nitride-yakagadzirwa nemhangura yemhangura inoratidza FE ye39 ± 2% yeC2H4, inodarika Cu yakachena (~ 23%) uye Cu (~ 28%).Inofanana neiyo yataurwa pamusoro Cu+/Cu catalytic system, boron yakashandiswa seheteroatom dopant kusuma nekudzikamisa Cuδ+ (41).Avhareji oxidation state yemhangura inogona kudzorwa kubva ku +0.25 kusvika +0.78 nekushandura kusanganiswa kweboron dopant.Kuwanda kwehuwandu hwematunhu kwakaratidza kuti maerekitironi akatamiswa kubva kumhangura kuenda kuboron, zvichitungamira kune dopant-induced inochajiswa nzvimbo dzemhangura.Iyo boron-doped mhangura yakaratidza yakawedzera kuumbwa simba re *CHO yepakati uye, nekudaro, yakadzvanya maitiro ekuenda kuC1 zvigadzirwa.Pamusoro pezvo, inogona kuwedzera kusarudzwa kune multicarbon hydrocarbons nekudzikira *CO dimerization reaction simba (Fig. 4D).Nokugadzirisa avhareji yepamusoro oxidation mamiriro emhangura, yakakwirira C2 FE ye ~ 80% ne ~ 53% C2H4 inogona kuwanikwa pasi pevhareji yemhangura oxidation state ye +0.35 (Fig. 4E).Kusvika iye zvino, nzvimbo dzinoshanda pamhangura dzakaonekwa seCu0, Cuδ+, uye / kana maitiro avo eECR mune zvidzidzo zvakasiyana (39, 41, 42, 81, 82).Nekudaro, ndeipi saiti inoshanda ichiri kukakavara.Nepo iyo heteroatom doping-induced Cuδ+ catalysts yakaratidzwa kuve inoshanda zvakanyanya kuECR yakanangana neC2+ zvigadzirwa, iyo synergistic mhedzisiro kubva panguva imwe chete inogadzirwa hurema uye mainterface inofanirwa kutariswa.Nekudaro, yakarongeka mune operando maitiro anofanirwa kuvandudzwa kuti aone nzvimbo inoshanda pamhangura uye kutarisa inogona kuitika mune situ shanduko yenzvimbo dzinoshanda pasi pemamiriro ekuita.Kunze kwezvo, kugadzikana kwemhangura yemhangura yakanaka ndeimwe kunetseka pasi pemamiriro ekuderedza electrochemical.Maitiro ekugadzira macatalysts ane yakagadzikana Cuδ+ saiti inoramba iri dambudziko.

(A) Pfupiso yeC2H4 kusarudzwa kwezvakasiyana plasma-activated copper catalysts.Yakadhindwa nemvumo kubva kuNature Publishing Group (37).Scale mabara, 500 nm.(B) Ratio yeCu oxidation inotaura maererano nenguva yekuita pa -1.2 V inopesana neRHE mu electroredeposited mhangura.Yakadhindwa nemvumo kubva kuNature Publishing Group (61).(C) Ratio yeCu + marudzi ane basa rekuita nguva pa -0.95 V inopesana neRHE muCu-on-Cu3N kana Cu-on-Cu2O.Yakadhindwa nemvumo kubva kuNature Publishing Group (81).(D) Boron doping yakakwanisa kushandura avhareji adsorption simba reCO munzvimbo yemhangura uye kudzikisa simba reCO─CO dimerization.1[B], 2[B], 3[B], 4[B], uye 8[B] zvinoreva kuwanda kwe subsurface boron doping mu copper catalysts, yaive 1/16, 1/8, 3/ 16, 1/4, uye 1/2, zvichiteerana.(E) Ukama huri pakati peiyo oxidation state uye FE yeC2 kana C1 zvigadzirwa mu boron-doped copper catalysts.(D) uye (E) anodhindwa zvakare nemvumo kubva kuNature Publishing Group (41).(F) SEM mifananidzo yemafoiri emhangura ane makobvu akasiyana eCu2O mafirimu pamberi (pamusoro) uye mushure (pasi) ECR.Yakadhindwa nemvumo kubva kuAmerican Chemical Society (83).

Kunze kweiyo yemagetsi chimiro, oxide-yakatorwa zvinhu zvinogona zvakare kutungamira kune morphology kana chimiro shanduko panguva yekudzikisa in situ.Kubva pakuona kwe morphology kana chimiro, iyo yakakwidziridzwa electrochemical kuita kweoxyde-inotorwa electrocatalysts yakanzi yakakonzerwa nekuumbwa kwezviyo zvinoshanda miganhu, mipendero, uye nhanho (83-85).Yeo nevashandi pamwe navo (83) vakashuma yakasarudzwa C─C coupling pane electrodeposited Cu2O mafirimu ane ukobvu hwakasiyana (Fig. 4F).In situ Raman spectroscopy yakaratidza kuti pamusoro pemafirimu eCu2O akaderedzwa kuita yakagadzika simbi Cu0 panguva yeECR (83).Nekuda kweizvozvo, simbi Cu0 yakasimbiswa secatalytic inoshanda nzvimbo panzvimbo yeCu + marudzi kana iyo Cu +/Cu0 interface.Mukuita kudzikisa Cu2O kuita simbi Cu0, iyo inokonzeresa nzvimbo inogona kunge iri mune situ kuita nhanho, mipendero, uye maturu.Yakataridzwa kuti matanho akaumbwa uye mipendero inoshanda zvakanyanya kupfuura materesi, anobva pakusunga kwavo kwakasimba ne * CO, iyo inogona kuwedzera hydrogenate * CO kusvika * C H O kana * CH2O.Kunze kwezvo, edge Cu maatomu anosimudzira kusimudzira *CHO uye *CH2O kuumbwa.Basa rakapfuura rakakurudzira kuti * CHO uye * CH2O vepakati vanonyanya kufarira C─C kubatanidza pane * CO mune kinetics (86).Nekugadzirisa iyo yepamusoro morphology, iyo chemisorption masimba e *CHO uye * CH2O epakati anogona kugadzirwa.Muchidzidzo ichi, vanyori vakaona kuti FE yeC2H4 yakaderera kubva pa40 kusvika ku22% pavakawedzera kukora kweCu2O firimu yakaonda kubva ku0.9 kusvika ku8.8 μm.Izvi zvinokonzerwa neiyo yakaderera yakarongeka Cu iyo yakawedzera nekuwedzera kweCu2O ukobvu.Aya maatomu asina kubatanidzwa anogona kusunga neH uye, nekudaro, anonyanya kufarirwa kushanduka kwehydrogen pane kubatana kweC─C.Iri basa rakaratidza kuti iyo oxide-yakatorwa mhangura catalyst inogona kuwedzera zvakanyanya iyo C2H4 kusarudzwa kuburikidza nepamusoro morphology kuvaka pane kuunza inochajwa Cuδ+ marudzi.Kushandisa oxide-derived catalysts, ethane (C2H6) yakave yakagadzirwawo zvakasarudzwa nerubatsiro rwepalladium (II) chloride (PdCl2) inowedzera mu electrolyte (34).Yakaratidza kuti adsorbed PdClx pamusoro peCu2O-yakatorwa Cu yakaita basa rakakosha kuC2H6 shanduko.Kunyanya, CO2 yakatanga kuderedzwa kusvika kuC2H4 paCu2O-yakatorwa inoshanda Cu nzvimbo, uye ipapo yakaumbwa C2H4 yaizove hydrogenated nerubatsiro rwe adsorbed PdClx kugadzira C2H6.Iyo FE yeC2H6 yakawedzera kubva <1 kusvika 30.1% nerubatsiro rwePdCl2.Iri basa rinoratidza kuti kusanganiswa kweiyo yakanyatsotsanangurwa ECR catalyst uye electrolyte yekuwedzera inogona kuvhura mikana mitsva yeC2 + chaiyo chigadzirwa chizvarwa.

Morphology uye / kana chimiro chemutemo chinomiririra imwe nzira yekumisikidza catalytic selectivity uye chiitiko.Kudzora saizi, chimiro, uye akafumurwa maficha ezvinokonzeresa zvakaratidzwa zvakanyanya kune ECR kuita kuvandudza (58, 87, 88).Semuenzaniso, iyo Cu(100) facet inosarudzirwa kuchizvarwa cheC2H4, nepo chigadzirwa chinotungamirwa kubva kuCu (111) catalyst ndeye methane (CH4) (87).Muchidzidzo cheCu nanocrystals ane maumbirwo akasiyana-siyana uye hukuru, Buonsanti uye vashandi pamwe chete (58) vakaratidza kutsamira kwehukuru hwe-nonmonotonic yeC2H4 selectivity mu cube-shaped copper nanocrystals (Fig. 5A).Mukati, cubic Cu nanocrystals yakaratidza yakakwira C2H4 chiitiko uye kusarudza kupfuura spherical Cu nanocrystals nekuda kwekukosha kweiyo (100) facet.Iyo diki yekristaro saizi yecubic Cu inogona kupa chiitiko chepamusoro nekuda kwekuwedzera kuungana kwepasi-yakarongeka nzvimbo dzepasi, senge makona, nhanho, uye kinks.Nekudaro, iyo yakasimba chemisorption yepasi-yakarongeka nzvimbo yakaperekedzwa nepamusoro H2 uye CO selectivity, zvichikonzera yakaderera yakazara hydrocarbon FE.Kune rumwe rutivi, chiyero chenzvimbo dzepamucheto kune nzvimbo dzendege yakaderera nekuwedzera kwezvikamu zviduku, izvo zvinokanganisawo kushanda kweC2H4 kugadzirwa.Vanyori vakaratidza kuti yepakati-saizi mhangura nanocubes ine 44-nm kumucheto kureba yakaratidza yakakwira C2H4 sarudzo nekuda kweiyo optimized chiyero pakati pehukuru hwechikamu uye density yemasaiti ekumucheto.Uyezve, morphology inogonawo kukanganisa pH yemunharaunda uye kutakura kwevanhu vakawanda panguva yeECR.Izvo zvakaratidzwa kuti iyo yakakwirira yemunharaunda pH iri padyo necatalyst surface, iyo inokonzerwa neiyo in situ yakagadzirwa OH-, inodzvinyirira iyo proton-inobatanidzwa yekuita nzira.Nekuda kweizvozvo, C2+ hydrocarbon formation kuburikidza ne *CO dimerization inogona kuvandudzwa, uye CH4 inoumbwa kuburikidza ne *COH yepakati inogona kuvharwa.Copper nanowire arrays (Fig. 5B) yakaratidzwa kuti iwane yakawedzera pH yemunharaunda (68).Se electrolyte inowanzo shandiswa, CO2 saturated potassium bicarbonate (KHCO3) solution ichakurumidza kukanganisa OH- (HCO3- (HCO3-+ OH- = CO32- + H2O) uye kuderedza pH yemunharaunda.Nekurebesa microstructure, kupararira kweHCO3- muCu nanowire arrays kunogona kuderedzwa neimwe nzira kuitira kuti neutralization effect yeOH yemunharaunda - ichadzvinyirirwa kune imwe nhanho.Pahwaro hwenheyo yakafanana, meshes yemhangura ine mesopores yakanyatsodzorwa (Fig. 5C) yakaratidza kukwidziridzwa FE yeC2H4 kana C2H6 kugadzirwa (32).Yakaratidza kuti pH yenzvimbo munzvimbo ye electrode inogona kuwedzerwa nekudzikisa upamhi hwepore, zvichikonzera kudzikira kweC1 chigadzirwa FE uye kuwedzera C2 chigadzirwa FE.Kunze kwezvo, nekuwedzera kudzika kwepore, chigadzirwa chikuru chekudzikisa chinogona kugadzirwa kubva kuC2H4 kuenda kuC2H6.Iyo FE yeC2H6 yaive yakakwira se46%.Sezvo makemikari akavharirwa mukati me pores panguva yeECR, nguva yakareba yekuchengetedza nguva yepakati yakakosha inokonzerwa nehupamhi yakadzika pores yakatsanangurwa sechikonzero chikuru chekusarudzwa kwepamusoro kune yakazara C2 hydrocarbon.CuI-yakatorwa Cu nanofibers yakaratidzawo high selectivity kuenda kuC2H6 (FE = 30% pa -0.735 V versus RHE) (89).Iyo anisotropic morphology uye yakakwirira pamusoro roughness yeCuI-yakatorwa Cu nanofibers inogona kuvandudza kugona kwekuteya kweH2 yakabatwa uye nokudaro kuwedzera FE yeC2H6.

(A kusvika C) Morphology kana maitiro ekugadzirisa.(A) Density yemaatomu (left axis) uye chiyero chemaatomu kumucheto kwesaiti (Nedge) kumaatomu ari pa (100) ndege (N100) (kurudyi axis) zvinoenderana nehurefu hwekumucheto (d).Yakadhindwa nemvumo kubva kuna John Wiley naVanakomana (58).(B) Scheme ye morphology yakakonzera pH kuchinja.Yakadhindwa nemvumo kubva kuna John Wiley naVanakomana (68).(C) Kusarudzwa kwechigadzirwa kwemesopore mhangura ine hukuru hwakasiyana hwepore uye kudzika.Yakadhindwa nemvumo kubva kuna John Wiley naVanakomana (32).(D kusvika H) Ligand mhedzisiro.(D naE) ECR pacopper nanowire (Cu NW) ine marudzi akasiyana emaamino acids (D) kana mamodhifita (E) pa −1.9 V. Yakadhindwazve nemvumo kubva kuRoyal Society of Chemistry (35).(F) Mitengo yekugadzira yeC2H4 mune dzakasiyana halide electrolytes ine akasiyana adsorption mikana paCu (35).Yakadhindwa nemvumo kubva kuAmerican Chemical Society (91).NHE, yakajairika hydrogen electrode.(G) FE yeC2H4 uye CO muzvikamu zvakasiyana zveKOH electrolytes uye (H) Tafel slope yeC2H4 muzvikamu zvakasiyana zveKOH electrolytes.(G) uye (H) akadhindwa kubva kuAmerican Association for the Advancement of Science (AAAS) (33).

Catalyst pamusoro pekugadzirisa uchishandisa mamorekuru madiki ndeimwe nzira inozivikanwa yekuvandudza mashandiro emagetsi eECR.Iyi sarudzo inogona kukanganisa microenvironment pedyo ne catalyst surface, iyo inogona kudzikamisa makiyi epakati nekuda kwekubatana pakati pepamusoro ligand uye yepakati.Amine yakashumwa sechigadziriso chekusimudzira ECR (35).Akasiyana-siyana amino acids, anosanganisira glycine (Gly), dl-alanine (Ala), dl-leucine (Leu), dl-tryptophan (Tyr), dl-arginine (Arg), uye dl-tryptophan (Trp), akaongororwa kuti dzidza maitiro avo pamhangura nanowires (35).Sezvakaratidzwa muFig. 5D, ose amino acid-based ligands akakwanisa kuvandudza kusarudzwa kweC2 + hydrocarbons.Kukwidziridzwa kwakadaro kunoratidza kuti ─COOH uye ─NH2 mashandiro emapoka muamino acid anogona kunge ane basa rekuwedzera kusarudzwa kweECR.Mishumo yapfuura yakaratidza kuti adsorption yeamino acids paCu uso yakawanikwa kuburikidza ese ─COOH uye ─NH2 mapoka (35, 90).Stearic acid (C17H35COOH, RCO2H), iyo ine chete ─COOH boka, yakasarudzwa kuti ione basa re ─COOH.Mamwe madhifita, akadai sea-anthraquinone diazonium munyu (AQ), o-nitrobenzene diazonium munyu (PhNO2), uye dodecyl mercaptan (C12H25SH, RSH), isina ─COOH kana ─NH2 mapoka, akaongororwawo.Zvisinei, vose vakanga vasina kunaka kweC2 + hydrocarbon FE kunatsiridza (Fig. 5E).Theoretical calculations dzakaratidza kuti ─NH3+ mapoka ari adsorbed zwitterionic glycine anogona kudzikamisa *CHO yepakati nekuda kwekudyidzana kwakasimba, senge hydrogen bond.Kuiswa kwehalide ions mu electrolyte ndiyo imwe nzira yekushandura macatalysts (91, 92).Sezvakaratidzwa muFig. 5F, C2H4 chiyero chekugadzira pa plasma-activated Cu inogona kuwedzerwa zvakanyanya nerubatsiro rwe halide additives.Zvakaratidzwa kuti I-ion inoshanda zvakanyanya kupfuura Br- uye Cl-, mukubvumirana neinowirirana adsorption simba reI-, Br-, uye Cl- paCu (100) facet (91).Kunze kwehalides, hydroxide ion yakaratidzawo maitiro akanaka paC2H4 kusarudza.Munguva pfupi yapfuura, Sargent uye vashandi pamwe chete (33) vakashuma CO2-to-C2H4 kutendeuka ne ~ 70% FE vachishandisa concentrated potassium hydroxide (KOH) electrolyte (kusvika ku10 M) musero rinoyerera.Sezvinoratidzwa muFig. 5G, kukwanisa kwekutanga kweCO neC2H4 mu10 M KOH electrolyte yakanga yakaderera zvikuru kana ichienzaniswa neyo mu1 M KOH.Uyezve, materu eTafel (Fig. 5H) yeC2H4 formation yakaderera nekuwedzera kwe hydroxide concentration (135 mV decade-1 mu 1 M KOH uye 65 mV makore gumi-1 mu 10 M KOH), zvichiratidza kuchinja kwehuwandu hwehuwandu- danho rekusarudza.Density functional theory (DFT) mhedzisiro yakaratidza kuti kuvapo kweiyo concentrated hydroxides kunogona kudzikisa simba rinosunga reCO yepakati uye zvakare kuwedzera kusaenzana kwechaji pakati pemaatomu maviri ekabhoni mune adsorbed OCCO yepakati.Nekuda kweizvozvo, iyo OCCO yepakati yaizowedzera kudzikamiswa kuburikidza neakasimba dipole kukwezva, zvichitungamira kune yakaderera activation simba chipingamupinyi cheCO dimerization, izvo zvinozovandudza kuita kwese.

C2+ oxygenates senge ethanol (CH3CH2OH) chimwe chikamu chikuru chezvakanyanya kukosha ECR zvigadzirwa.Indasitiri synthesis ye ethanol isimba-rine simba rekuita, iro rinodya zvakare yakawanda yakawanda ethylene kana yekurima feedstocks (40).Nokudaro, electrocatalytic kugadzirwa kwe ethanol kana imwe C2 + oxygenates kubva ku CO2 inoita zvakawanda zvehupfumi uye zvakatipoteredza pfungwa.Sezvo chizvarwa che ethanol kubva kuECR chakagovanisa penultimate yepakati neC2H4 iyo iri *C2H3O (43), kusarudza hydrogenation yepakati iyi inogona kushandura ECR nzira kubva kuC2H4 kuenda kudoro (64).Zvisinei, mune dzakawanda masisitimu, kusarudzwa kweC2 + oxygenates kwakaderera zvakanyanya kupfuura mahydrocarbons (31, 37, 39, 41, 42, 67).Nokudaro, muchikamu chino, tichasimbisa maitiro ekugadzira electrocatalyst anogona kuwana inoshamisa C2 + oxygenate FE inopfuura 25%.

Sezvakakurukurwa pamusoro apa, yakanyatsogadzirwa bimetallic catalysts inogona kuvandudza kusarudzwa uye basa reC2 + hydrocarbon production.Imwe nzira yakafanana asi isina kufanana yakashandiswawo kuvandudza kushanda kwe electrocatalytic yeC2 + oxygenates (38, 93, 94).Semuenzaniso, Ag-incorporated Cu-Cu2O catalysts yakaratidza tunable ethanol selectivity, uye yepamusoro-soro ethanol FE yaive 34.15% (95).Muganho webiphasic muchikamu-chakasanganiswa Ag-Cu alloy, pachinzvimbo cheAg/Cu atomic ratio, yakaonekwa sechinhu chakakosha chekusarudza kugadzirwa kwe ethanol.Sezvo iyo Cu saiti iri padyo neiyo Ag saiti muchikamu-yakasanganiswa pateni (Ag-Cu2OPB), chiyero chekugadzira ethanol chepakati cheiyo chikamu-yakasanganiswa sampu inogona kusimudzirwa mukuenzanisa nechikamu-chakaparadzaniswa (Ag-Cu2OPS). ), zvichitungamira kune zvirinani ethanol chizvarwa kuita.Kunze kwe ethanol, Cu-Ag bimetallic NPs yakaratidzawo kushandura CO2 kuti acetate pamwe nekuwedzera kwe benzotriazole (93).Pa -1.33 V inopesana neRHE, FE yeacetate yaiva 21.2%.Nzira mbiri dzinogona kuita nzira dzakatsanangurwa munyaya iyi: Imwe yakavakirwa paCO dimerization, uye imwe yacho iri pakuisa CO, ichiratidza basa rakakosha reCO yepakati kuumbwa pane anoshanda Ag masaiti.Kucherechedza kwakafanana kwakashumwa muCu-Zn catalysts (Fig. 6, A uye B) yekugadzirwa kwe ethanol (38).Nekugadzirisa zviri muZn muZn-Cu alloyed catalysts, chiyero che ethanol maringe neC2H4 FE chinogona kudzorwa zvakanaka muhuwandu hwe0.48 kusvika 6, zvichiratidza kukosha kweCO-evolving nzvimbo dzeC2 + oxygenate formation.Kugadzirwa kwealloyed catalysts kunogona kukonzeresa kunetsa pane matrix zvinhu, izvo zvingave zvisingadiwe dzimwe nguva.Saka, nzira yakananga inoenda kune bimetallic catalysts inogona kuve yakakodzera kune zvimwe zvinonangwa zvigadzirwa.Jaramillo nevashandi pamwe navo (96) vakagadzira yakapfava Au-Cu bimetallic system, yakagadziridzwa nekuiswa kwakananga kwegoridhe NPs pane polycrystalline Cu foil, kuti vaongorore tandem catalysis mhedzisiro.Iyo bimetallic Au-Cu yakaratidza synergistic selectivity uye chiitiko chakanangana neC2+ zvinwiwa zvinodhaka, kupfuura zvakachena mhangura negoridhe, uye Au-Cu alloy.Kuenzaniswa neCu foil, iyo bimetallic Au-Cu system yakaratidza kuwedzera kwenharaunda yeCO concentration nekuda kwekuvapo kweAu NPs (Fig. 6C) iyo yakashanda kune CO chizvarwa.Sezvo goridhe isiri kushanda mukuderedza CO, iyo yakakwidziridzwa C2 + chiyero chekugadzira doro paAu-Cu bimetallic catalysts yakapihwa kune tandem catalysis michina.Kunyanya, maNPs egoridhe anogona kuburitsa yakakwira CO yemuno padhuze neCu pamusoro.Tevere, akawanda emunharaunda CO mamorekuru anogona kuderedzwa kusvika kuC2+ doro neCu.

(A kusvika C) Alloy mhedzisiro.(A) Maximum FE ye ethanol uye C2H4 uye FE chiyero che ethanol uye ethylene pane akasiyana Cu-Zn alloys.(B) Chikamu chemazuva ano density ye ethanol pane akasiyana Cu-Zn alloys.(A) uye (B) anogadzirwazve nemvumo kubva kuAmerican Chemical Society (38).(C) CO2 kuderedza uye CO kushanduka kwemazinga pagoridhe, mhangura, uye Au-Cu bimetallic system.Yakadhindwa nemvumo kubva kuNature Publishing Group (96).(D kusvika L) Morphology kana maitiro ekugadzirisa.(D) Schematic mufananidzo wesimbi ion bhasikoro nzira.(E uye F) SEM mifananidzo ye100-kutenderera Cu pamberi (E) uye mushure (F) prereduction pasi peECR mamiriro.(G) TEM uye yakasarudzwa-nzvimbo maerekitironi diffraction yakaratidza kuti Cu(100) yakafumurwa uye (H) yemahara simba re*OCCO uye *OCCHO kugadzirwa paCu(100), Cu(111), uye Cu(211) maface.(D) kusvika (G) anoburitswa nemvumo kubva kuNature Publishing Group (42).(I) Ratio yeokisijeni uye mahydrocarbon sekushanda kwezvinogona kuitika paCu (111), Cu (751), uye Cu (100).(J) Nhamba dzeCoordination dzeCu(111), Cu(100), uye Cu(751).(I) uye (J) anodhindwa nemvumo kubva kuNational Academy of Sciences (97).(K) Scheme yekushandura maitiro kubva kuCu NPs kuenda kucubic-semhangura.Yakadhindwa nemvumo kubva kuNational Academy yeSainzi (98).(L) SEM mifananidzo ye nanodendritic mhangura pamberi uye mushure meECR.Yakadhindwa nemvumo kubva kuAmerican Chemical Society (99).

Kusarudzwa kuratidzwa kwekristaro maficha emagetsi emagetsi kwakaratidzwa senzira inoshanda uye yakatwasuka yekuwana yakakwidziridzwa FE kune chaiyo ECR zvigadzirwa uye yakakosha nzira yekunzwisisa kwakakosha.Yakareruka asi scalable synthesis yeimwe-crystal catalysts inonetsa.Yakafuridzirwa ne galvanostatic charging-discharging (GCD) maitiro emabhatiri, boka redu rakagadzira simbi ion cycling nzira (Fig. 6D) kuti zvisarudze kufumura crystal facet yeCu catalyst (42).Mushure me100 GCD cycles, dense Cu nanocube array yakaumbwa paCu foil ine pachena (100) facets (Fig. 6, E kusvika G).Iyo 100-cycle catalyst yakaratidza yakazara C2+ doro FE inodarika 30% uye inoenderana C2+ doro ikozvino density inodarika 20 mA cm−2.Nekudaro, iyo gumi-kutenderera Cu ine yakaderera reshiyo ye (100) facet yakangopa C2+ doro FE ye ~10%.DFT simulation yakasimbisa kuti Cu (100) uye yakatsika (211) mafaces aive akanakira C─C coupling pamusoro peCu (111), sezvakaratidzwa muFig. 6H.A modhi catalyst, epitaxial Cu firimu ine akasiyana akafumurwa maficha, yakashandiswa kuona inoshanda-saiti motifs yakanangana neC2 + oxygenate kugadzirwa (Fig. 6I) (97).Sezvo zvisingaite zvishoma kuti CO* dimer ive padhuze neH* maatomu pamusoro penzvimbo ine vavakidzani vashoma, nzvimbo dzakaderera-dzakarongwa dzeCu dzinogona kudzvanyirira kuumbwa kwemahydrocarboni uye kutungamirira kukuvandudzwa kweC2+ oxygenate FE nekuti yakanyanya kuoma kuita hydrogenate. C─C yakabatanidza ECR pakati pepamusoro payo (97).Mune epitaxial Cu firimu yekudzidza, vanyori vakasimbisa kuti ECR paCu (751) facet yakaratidza yakagadziridzwa oxygenate / hydrocarbon ratio.Kuwedzeredzwa uku kunogona kuverengerwa pamusoro peCu atomu geometry yemhando dzakasiyana dzeCu uye inoenderana yakaderera avhareji nhamba yakarongeka (Fig. 6J), uko Cu atomu yakarongeka, zvichiteerana, nevaviri, vana, uye vatanhatu vavakidzani vepedyo paCu(751), Cu(100), uye Cu(111) zvikamu.In situ morphology reconstruction yakashandiswawo kuvandudza C2+ oxygenate FE.Inoshanda cube-seCu catalyst yakagadzirwa naYang uye vashandi pamwe chete (98), iyo yakaratidza kuvandudzwa kweC─C yekubatanidza kuita.Mune zvakadzama, monodisperse Cu NPs (6.7 nm) ine zvakasiyana-siyana zvakarodha zvakaiswa pane kabhoni bepa rutsigiro sechinhu chinokonzeresa ECR.Zviripachena, yakawedzera FE yeC2 + oxygenates yakaonekwa nekuwedzera kweCu NP kurodha.Zvakaratidzwa kuti densely akazara Cu NPs pasi yakakwirira loading ezvinhu akapinda mu situ morphological shanduko panguva ECR, umo cube-kufanana morphologies vakapedzisira kuumbwa (Fig. 6K).Ichi chichangobva kuumbwa chimiro chakawanikwa chichiwedzera electrocatalytically active.Tafel ongororo yakaratidza kuti CO dimerization yaive nhanho-yekutarisa nhanho yeC2 kuumbwa kwechigadzirwa, nepo iyo yen-propanol yakaratidza nzira yakasarudzika mune ino catalytic system.Nanodendritic mhangura mumwe muenzaniso unoratidza kukosha kwekugadzirisa morphology yeC2 + oxygenate production (99).Muchidimbu, FE yose yemhangura yakanyatsotsanangurwa nanodendrite (Fig. 6L) yeC2 + doro yaiva inenge 25% pa -1.0 V inopesana neRHE.An inoshamisa n-propanol FE ye13% inogona kuwanikwa pa -0.9 V. Tichifunga nezvebasa rakakwirira reCu atomu, copper-based catalysts nguva dzose inotambura nekuparara kwemaitiro panguva yeECR, kunyanya pakunyanya kudarika, izvo, zvakare, zvinotungamirira kuvarombo. kugadzikana.Zvisinei, mhangura yakadaro nanodendritic yakaratidza kugadzikana kwakanaka kwekugadzirwa kwedoro, ichiratidza doro FE ye ~ 24% pamusoro pemaawa matanhatu.

Kukanganisa kwema electrocatalysts, akadai seatomu vacancies uye dopants, anoratidza mukana wekushambadza zvisina kujairika ECR intermediates uye, nekudaro, nekusarudza kusimudzira inoenderana nzira inoenda kune oxygenates (29, 43, 100).Kutora * C2H3O semuenzaniso, iyo inogona kunge iri peultimate yepakati ye ethylene uye ethanol kugadzirwa, Sargent uye vashandi pamwe chete (43) vakadzidza basa rekuremara mu-core-shell Cu electrocatalyst zvakadzama.Ivo ne theoretically vakaratidza kuti kuita kwesimba zvipingamupinyi zve ethylene uye ethanol kuumbwa kwakafanana mukutanga C─C coupling stage (0.5-V overpotential) (Fig. 7A).Pasi pemamiriro ezvinhu akadaro, kuiswa kwemhangura yemhangura kwaizowedzera zvishoma simba rekudzivirira kuti ethylene paumbwe, asi haina kuratidza simba pamusoro pechizvarwa che ethanol (Fig. 7B).Zvisinei, sezvinoratidzwa muFig. 7C, copper catalysts ine vacancy uye subsurface sulfur dopant inogona kuwedzera zvakanyanya simba rekuvhara nzira ye ethylene, zvichiita kuti ive isingafadzi thermodynamically.Zvisinei, kuchinjwa kwakadaro kwakaratidza kusakosha kwemaitiro ethanol nzira.Chiitiko ichi chakaongororwa zvakare.A core-shell yakarongeka Cu2S-Cu ine nzvimbo dzakawanda dzepamusoro (Cu2S-Cu-V; Fig. 7D) yakagadzirwa.Chiyero chedoro kune ethylene chakawedzera kubva pa 0.18 pane isina Cu NPs kusvika 0.34 pane vacancy-isina Cu2S-Cu uyezve kusvika 1.21 paCu2S-Cu-V, kunyange zvazvo FE yose yeC2 + zvigadzirwa zvezvose zvinogadzirisa zvakaramba zvakafanana (Fig. 7E) .Uku kucherechedzwa kwakaratidza kuti kukwidziridzwa kwedoro selectivity kwakabatana nekudzvinyirirwa kwekugadzirwa kwe ethylene, zvinoenderana nemhedzisiro yeDFT.Uye zvakare, hurema huinjiniya hunoita basa rakakosha resimbi-isina kabhoni catalyst sezvo yakachena kabhoni zvinhu zvisingashande kune ECR.Dopants dzakadai senitrogen uye boron zvakashandiswa kushandura chimiro chemagetsi che carbon-based catalyst (31, 43, 100).Semuenzaniso, nitrogen-doped nanodiamond (NDD) firimu pasilicon substrate yakabviswa naQuan et al.(29) yekusarudza acetate kugadzirwa kubva ECR (Fig. 7F).Iyo acetate yekutanga inogona kunge yakaderera se -0.36 V kupesana neRHE kushandisa NDD catalyst, uye FE yeacetate yakanga inopfuura 75% mune imwe nzvimbo inogona kubva -0.8 kusvika -1.0 V kupesana neRHE.Kuti unzwisise kwakabva kwekuvandudzwa kunoshamisa kwakadaro, NDD / Si electrodes ine nitrogen yakasiyana-siyana kana nitrogen mhando dzakagadzirirwa uye dzakaongororwa (Fig. 7G).Vanyori vakagumisa kuti kushanda kwepamusoro kweNDD / Si catalyst yeECR inogona kunge yakakonzerwa nepamusoro-soro ye hydrogen evolution uye N doping, apo N-sp3C mhando dzaive dzakanyanya kushanda pakugadzirwa kweacetate.Electrokinetic data uye in situ infrared spectrum yakaratidza kuti nzira huru yekugadzirwa kweacetate inogona kunge iri CO2 → *CO2− → *(COO)2 → CH3COO−.Kunze kwenitrogen, boron imwe heteroatom yakanyatsoongororwa kuti igadzirise chimiro chemagetsi che nanodiamond.Zvisinei, boron-doped nanodiamond (BDD) inonyanya kuderedza CO2 kune formaldehyde kana formate (101).Uyezve, Quan uye vashandi pamwe chete (102) vakaratidza kuti boron nenitrogen co-doped nanodiamond (BND) yakaratidza synergistic effect paECR, iyo inogona kukunda kudzikiswa kweBDD uye nekusarudza kubudisa ethanol.BND1, BND2, uye BND3 zvinokonzeresa zvine zvakasiyana nitrogen zviri mukati uye yakafanana boron doping mazinga akagadzirwa.Sezvinoratidzwa mumufananidzo 7H, iyo yakanyanya kusarudzwa ethanol kusvika ku93% inogona kuwanikwa paBND3 catalyst pa -1.0 V versus RHE, iyo ine yakanyanya nitrogen doping.Theoretical calculation yakaratidza kuti C─C coupling process paBND yaive yakanaka thermodynamically, apo boron atomu yakasimudzira kutorwa kweCO2 uye nitrogen dopant yakafambisa hydrogenation yepakati kuenda ethanol.Kunyange zvazvo heteroatom-doped nanodiamond yaikwanisa kushandura CO2 kuita multicarbon oxygenates ine high selectivity, basa rayo reECR rine zvishoma nekuda kwekunonoka kwechaji yekufambisa (yazvino density isingasviki 2 mA cm−2).Graphene-based material inogona kunge iri mhinduro yekukunda kukanganisa kwedhaimani-based catalysts.Nechepfungwa, iyo yekumucheto pyridinic N nzvimbo dziri mugraphene layer dzakatorwa senzvimbo dzinoshanda dzeC─C coupling (103).Izvi zvinokonzerwa nekuti kuvapo kwepyridinic N pamucheto nzvimbo kunogona kushandura CO2 kuita CO, iyo inogona kubatanidzwazve muC2 + molecule (Fig. 7I).Semuenzaniso, iyo *C2O2 yepakati inogona kudzikamiswa munitrogen-doped kabhoni umo maatomu maviri eC anosungirirwa kune pyridinic N neC atomu iri padyo, zvichiteerana (103).Kufanotaura kwedzidziso kwakabva kwasimbiswa uchishandisa nitrogen-doped graphene quantum dot (NGQD) catalysts (31).Mushure mekuputika kwe nitrogen-doped graphene sheets (1 kusvika 3 μm) (Fig. 7J), 1- kusvika 3-nm NGQDs yakawanikwa umo kuwanda kwepyridinic N pamucheto nzvimbo kwakawedzerwa nemirairo mitatu yehukuru.Pa -0.78 V kupesana neRHE, iyo yakawanda FE yeC2 + oxygenates inogona kusvika kusvika ku26%.Mukuwedzera, sezvinoratidzwa mumufananidzo 7K, chikamu chemazuva ano cheC2 + oxygenates chiri pedyo ne 40 mA cm-2 pa -0.86 V kurwisana neRHE, iyo yakakwirira kudarika iyo nanodiamond yakagadziridzwa.Mukuenzanisa, N-yemahara graphene quantum dots uye N-doped graphene oxide, iyo inoratidza yakaderera kumucheto saiti pyridinic N, inonyanya kuburitsa H2, CO, uye fomati.

(A kusvika C) Gibbs simba remahara kubva ku *C2H3O kuenda ku ethylene uye ethanol yemhangura, copper ine vacancy, uye mhangura ine copper vacancy uye subsurface sulfur.(D) Schematic mufananidzo weCu2S-Cu-V catalyst.(E) FE yeC2 + doro uye ethylene, pamwe chete neFE chiyero chedoro kune alkenes.(A) kusvika (E) anodhindwa nemvumo kubva kuNature Publishing Group (43).(F) SEM mufananidzo weNDD.(G) Mareti ekugadzirwa kweacetate uye fomati paNDD ine zvakasiyana nitrogen zviri mukati.pa%, atomic%.(F) uye (G) anogadzirwazve nemvumo kubva kuAmerican Chemical Society (29).(H) FEs dzeNDD, BDD, uye BNDs pa −1.0 V. Yakadhindwa nemvumo kubva kuna John Wiley and Sons (102).(I) Schematic mufananidzo wenzvimbo dzinoshanda dzeC─C kubatanidza muNGQDs.(I) inogadzirwazve nemvumo kubva kuAmerican Chemical Society (103).(J) TEM mufananidzo weNGQDs.Scale mabara, 1 nm.(K) Chikamu chazvino densities kune akasiyana zvigadzirwa uchishandisa NGQDs.(J) uye (K) anodhindwa nemvumo kubva kuNature Publishing Group (31).

Kupfuura maelectrocatalysts, electrode uye catalytic reactor architecture dhizaini inopa imwe nzira inoshanda yekusimudzira mashandiro eECR, kunyanya chiyero chekugadzira uye kushanda nesimba.Kuvandudzwa kwakakosha kwakaitwa padhizaini uye kugadzirwa kwemanovel electroreduction masisitimu kuti iwane yakanyatsoita kugadzirwa kweC2+.Muchikamu chino, tichakurukura ECR electrode / reactor dhizaini zvakadzama.

H-mhando maseru anoshandiswa zvakanyanya muyedzo yelab-scale, tichitarisa kuungana kwavo kuri nyore, kushanda kuri nyore, uye mutengo wakaderera.Masero akashongedzerwa neakazvimiririra cathode uye anode makamuri akabatanidzwa neion-exchange membrane (104, 105).Chinhu chikuru chakashata cheiyi H-mhando sero ndiyo yakaderera CO2 solubility muaqueous electrolyte, iyo inongova 0.034 M pasi pemamiriro ekunze, zvichiita kuti kuderedzwa kweCO2 kuderedzwa ikozvino j <100 mA cm-2 (64).Uyezve, zvimwe zvipingamupinyi zvemukati, zvinosanganisira nzvimbo shoma ye electrode uye nzvimbo yakakura yeinterelectrode, yatadza kuzadzisa zvinodiwa zvekutsvaga zviri kukura (105, 106).Nokuda kwekugadzirwa kweC2 +, masero eH-mhando anowanzoratidza kusarudzwa kwakaderera pasi pepamusoro pepamusoro, semuenzaniso, 32% ye ethylene pa -0.98 V versus RHE (107), 13.1% ye n-propanol pa -0.9 V versus RHE (99), uye 20.4% ye ethanol pa −0.46 V versus RHE (108), nekuda kwekukwikwidza kwakakomba kwehydrogen evolution.

Kugadzirisa nyaya dziri pamusoro apa, iyo inoyerera reactor yakatsanangurwa (15, 109).Mumaseru ekuyerera, gaseous CO2 rukova inogona kushandiswa zvakananga se feedstock pa cathode, zvichizotungamira kune yakanyanya kunatsiridza kuwanda kwekupararira uye chiyero chekugadzira (104, 110).Mufananidzo 8A unoratidza magadzirirwo akajairika esero rekuyerera, uko polymer electrolyte membrane (PEM) yakashanda seye electrode separator inoiswa pakati pematanho maviri ekuyerera.Iyo catalyst inovharirwa pane gasi diffusion electrode (GDE) kuti ishande se cathode electrode, umo gasi CO2 inopihwa zvakananga.Iyo catholyte, yakadai se 0.5 M KHCO3, inoramba ichiyerera mukati mehupamhi hutete pakati pe catalyst electrode nePEM.Pamusoro pezvo, divi reanode rinowanzotenderedzwa neaqueous electrolyte yeokisijeni evolution reaction (43, 110).Kuenzaniswa neH-mhando masero, aya membrane-based kuyerera maseru anoratidza hukuru hwepamusoro hweECR kuita.Semuenzaniso, Sargent uye vashandi pamwe chete (43) vakaongorora kushanda kweECR kweCu2S-Cu-V catalyst mune zvose H-type cell uye flow cell, sezvinoratidzwa mumufananidzo 8 (B kusvika E).Kushandisa H-mhando masero, iyo yakawanda FE yeC2 + zvigadzirwa yaiva 41% nehuwandu hwemazuva ano hwe ~ 30 mA cm-2 pasi -0.95 V kurwisana neRHE.Zvisinei, FE yeC2 + zvigadzirwa yakawedzera kusvika ku53% nehuwandu hwemazuva ano huri nyore kudarika 400 mA cm-2 pasi -0.92 V kurwisana neRHE muhurongwa hwekuyerera.Kuvandudzwa kwakakosha kwakadai kwekuita uchishandisa inoyerera reactor inogona kuverengerwa kune yakakwidziridzwa CO2 diffusion uye yakadzvanywa mativi maitiro, kunyanya kubva munharaunda gasi-electrolyte-catalyst katatu-interface architecture.

(A) Dhiyagiramu yekuyerera kwe electrolyzer ine zoomed-in schematic ye electrode-electrolyte interface.(A) inoburitswa nemvumo kubva kuna John Wiley neVanakomana (30).(B kusvika E) Kuenzanisa kweECR kushanda uchishandisa H-mhando sero uye kuyerera sero.(B) kusvika (E) anodhindwa nemvumo kubva kuNature Publishing Group (43).(F kusvika H) Maelectrolyte akasiyana anoshandiswa mumaseru ekuyerera achipesana nekuita kweECR.(F) kusvika (H) anodzokororwa nemvumo kubva kuna John Wiley naVanakomana (30).(I kusvika kuK) Chimiro uye kugadzikana kwekuita kwepolymer-based gasi diffusion electrode.(I) kusvika (K) anogadzirwazve nemvumo kubva kuAAAS (33).

Zero gap sero nderimwe boka riri kubuda remagetsi emagetsi, iro rinowedzera kubvisa nzira dzekuyerera mumaseru ekuyerera uye kudzvanya maelectrode maviri pamwe chete neion-exchange membrane pakati.Iyi gadziriso inogona kuderedza zvakanyanya kutamisa uye kuchinjisa maerekitironi uye nekudaro kunatsiridza kugona kwesimba, zvichiita kuti zvive nyore mukushandisa zvinoshanda (110).Iyo reactants inopihwa kune cathode inogona kunge iri CO2-yakazara catholyte kana humidified CO2 rwizi.Mupfunga wemvura kana aqueous electrolyte inopihwa kune anode kuti iburitse proton kutsiva muripo we CO2 yekuderedza mhando (111).Gutiérrez-Guerra et al.(109) yakaongorora mashandiro eCu-AC hybrid catalyst muzero gap cell ndokutaura kuti acetaldehyde ndicho chigadzirwa chikuru chine sarudzo yakakura ye60%.Seimwe mukana wemudziyo uyu, zviri nyore kwazvo kudzvanya kuyerera kweiyo reactant uye kuwedzera zvakanyanya iyo CO2 yekumisikidza yemuno, zvichikonzera hukuru hwazvino uye huwandu hwekuita (110).Nekudaro, iyo yakakurumidza ion yekutsinhana mwero mu zero gap maseru inoita kuti acidify iyo catholyte, ichichinja maitiro akananga H2 evolution panzvimbo ye CO2 kuderedza (112).Kuti vagadzirise dambudziko iri, Zhou nevashandi pamwe navo (112, 113) vakaisa buffer layer ine inotenderera aqueous electrolyte pakati pe cathode ne membrane kuchengetedza pH chaiyo pedyo ne cathode ye CO2 yekuderedza reaction.Kunyange zvazvo zvigadzirwa zvakasiyana-siyana zveC2 + zvakaonekwa pahwaro hwe zero gap masero, kusanganisira acetone, ethanol, uye n-propanol, maFEs achiri mashoma.Zvizhinji zvakashumwa zvidzidzo zvinogara zvichitarisa pane zvigadzirwa zveC1 zvinosanganisira huwandu hushoma hweproton uye erekitironi kutamiswa panguva yekudzikisa maitiro.Naizvozvo, kugona kwe zero gap cell yeC2+ zvigadzirwa zvichiri kupokana (110).

Zvakare, microfluidic electrolytic masero (MECs) imhando yeinoyevedza electrolyzer kumisikidzwa yakagadziriswa naKenis uye vashandi pamwe navo (39, 114).Muchigadzirwa ichi, membrane inotsiviwa nenzvimbo yakatetepa (<1 mm muukobvu) yakazadzwa nekuyerera kwe electrolyte stream kuti iparadzanise anode uye cathode.Mamorekuru eCO2 anogona kukurumidza kupararira mukati meiyo electrode-electrolyte interface pedyo necathode, uye maviri akagadzika maGDE anopeperetswa nekuyerera kweelectrolyte.Kuenzaniswa ne membrane-based kuyerera maseru, maMEC haangodzivise mutengo wakakwira membrane asi zvakare kudzikisira manejimendi emvura, izvo zvinonyanya kureva anode yakaoma-kunze uye mafashama ecathode kana ichishandiswa pakukwirira kwazvino nekuda kwekudhonza kwe osmotic kwemamorekuru emvura proton kutakura kubva anode kuenda kune cathode mhiri membrane (115).Sekuziva kwedu, zvisinei nekukodzera uye kubudirira kunoonekwa, huwandu hushoma hwezvidzidzo hwakawana zvigadzirwa zveC2+ mumaMEC ekutanga.Izvi zvichida zvinokonzerwa ne "inoyangarara" mhedzisiro yekuti mapurotoni akaumbwa muanode anodonhedzwa zviri nyore kubva munharaunda yecathode kana kushambidzwa neinoyerera electrolyte, pane kutora chikamu mune yakawanda proton inodiwa C2 + formation reaction.Kufungidzira kunogona kusimbiswa nemuenzaniso unotevera.Muna 2016, Kenis uye vashandi pamwe chete (31) vakarondedzera kubudirira kuderedzwa kwe CO2 kune C2 + zvigadzirwa pane yakagadziridzwa uye ine membrane-ine MEC, umo NGQDs inogona kuderedza CO2 molecules kuC2 + ne 55% FE (31% ye ethylene, 14% ye ethanol, 6% yeacetate, uye 4% yen-propanol) pane inoshandiswa inogona -0.75 V kupesana neRHE mu1 M KOH mhinduro.Zvakakosha kutaura kuti nharaunda ye electrolyte inogona kukanganisa zvakanyanya kusarudzwa kwechigadzirwa zvakare.Semuenzaniso, Jiao nevashandi pamwe navo (30) vakagadzira nanoporous Cu catalyst ndokuzoedza kuita kwayo ECR vachishandisa akasiyana maelectrolyte (KHCO3, KOH, K2SO4, uye KCl) mune membrane-based MEC.Vakaratidza kuti kuderedzwa kweCO2 mu alkaline electrolyte (KOH) kunoratidza kusarudzwa kwepamusoro kweC2 + uye kusimba kwemazuva ano, sezvakaratidzwa mumufananidzo 8 (F uye G).Pa -0.67 V maringe neRHE mu1 M KOH electrolyte, iyo FE yakawanikwa yeC2+ inosvika ku62% ine chikamu chemazuva ano density ye653 mA cm-2, iri pakati pehuwandu hwepamusoro-soro hwakambotaurwa mukuderedzwa kwe electrochemical CO2. yakanangana neC2+ zvigadzirwa.Ethylene (38.6%), ethanol (16.6%), uye n-propanol (4.5%) ndiyo mikuru yeC2 + michina ine zvishoma zveacetate.Vakaratidzawo kuti kune kuwirirana kwakasimba pakati pehuwandu hwepamusoro pH uye FE yeC2 + zvigadzirwa: Iyo yakakwirira yepamusoro pH, iyo yakakwirira yezvino densities uye C2 + zvigadzirwa zvinobereka, sezvinoratidzwa mumufananidzo 8H.Iko kuverenga kwe theoretical kwakaratidza kuti iyo yepedyo-yepamusoro OH- ions inogona kufambisa zvakasimba C─C coupling (31).

Pamusoro peiyo electrolyzer kumisikidzwa, iyo electrolyte yakaiswa mune akasiyana emagetsi anogona zvakare kushandura zvakanyanya ekupedzisira zvigadzirwa zveECR.Sezvatataura pamusoro apa, yakanyanya alkaline KOH mhinduro dzinogara dzichishandiswa mumaseru ekuyerera ane mashandiro akanaka kwete mumaseru emhando yeH.Izvo zvinoverengerwa kune chokwadi chekuti KOH electrolyte inogona kupa yakakwirira electrolyte conductivity, kuderedza ohmic kuramba pakati peiyo yakatetepa electrolyte coating pane catalyst uye yakawanda electrolyte, uyezve kuderedza inodiwa overpotentials yeC2+ kuumbwa (31).Mhedzisiro yeDFT inosimbisa zvakare kuti kuvepo kweOH-ion kunogona kuderedza simba rekudzivirira kweCO dimerization, nekudaro kuwedzera kuumbwa kweC2 + uye kudzvanyirira makwikwi kubva kuC1 uye H2 kuumbwa (30, 33).Nekudaro, alkaline KOH haigone kushandiswa se electrolyte muH-mhando maseru.Izvi zvinodaro nekuti CO2 hova dzinokurumidza kuita neKOH mhinduro uye pakupedzisira kugadzira bicarbonate mhinduro ine kwayakarerekera pH muH-mhando maseru (30).Mumaseru ekuyerera, zvisinei, kana CO2 yapararira kuburikidza neGDE, mamorekuru eCO2 anopedzwa pachikamu chemuganho wetatu (CO2-catalyst-electrolyte) kugadzira zvigadzirwa zvakaderedzwa nekukurumidza.Kunze kwezvo, kusabatika zvakanaka kwe electrolyte kunokwanisa kukurumidza kuwedzera pH yakatenderedza electrode mumagadzirirwo emagetsi emagetsi akamira, nepo kuyerera kwe electrolyte kunozorodza pamusoro uye kuderedza pH kushanduka mu electrolyte (33, 116).

Sezvambotaurwa kuti ECR ndeyekupararira-inodzorwa maitiro, yakakwira reaction pressure inogonawo kuwedzera zvakanyanya kuwanda uye interface CO2 kusungwa.Iwo akajairika high-pressure reactors akafanana nesimbi isina simbi autoclave, umo high-pressure CO2 (kusvika 60 atm) inogona kuiswa muchitokisi, zvichikonzera kuwedzera kunoshamisa mune zvese zviri zviviri FE uye density iripo yeC2+ (117). , 118).Sakata nevanoshanda navo (119) vakaratidza kuti density iripo inogona kuvandudzwa kusvika 163 mA cm−2 pasi pe30 atm paCu electrode ine ethylene sechigadzirwa chikuru.Mazhinji masimbi anokonzeresa (semuenzaniso, Fe, Co, uye Ni), pasina basa reC2 + kugadzirwa pakumanikidzwa kwakadzikama, anogona kuderedza CO2 kune ethylene, ethane, propane, uye zvimwe zvakakwirira-kurongeka C2 + zvigadzirwa pakumanikidzwa kwakakwirira.Izvo zvakaratidzwa kuti kusarudzwa kwezvigadzirwa zvakanyanya kunoenderana ne CO2 kudzvanywa nenzira yekushandura CO2 kuwanikwa panzvimbo ye electrode (117, 120).Zvigadzirwa zvikuru zvakaderedzwa zvinoshandurwa kubva kuH2 kusvika kumahydrocarbons (C2 + inosanganisirwa) uye pakupedzisira kuenda kuCO/HCOOH nekuwedzera CO2 kudzvanywa.Zvinonyanya kukosha, iyo CO2 kudzvanywa kunofanirwa kunyatsotariswa nekuti yakawandisa yakakwira kana yakaderera CO2 kumanikidza kunogona kukonzera yakawandisa kana kushomeka CO2 diffusion rate, iyo inowanzofarira kugadzirwa kweCO/HCOOH kana H2.Chete huwandu hunoenderana hwepakati CO uye yazvino density iyo yakagadzirwa pamusoro pe electrode inogona kufambisa iyo C─C yekubatanidza maitiro uye kuwedzera C2 + chigadzirwa kusarudza (119).

Kugadzira novel electrode ine zvimiro zvepamberi ndeimwe nzira yakakosha yekusimudzira yakasarudzika C2 + kugadzirwa.Pakutanga, maelectrodes anoshanda haasi masimbi esimbi uye anotambura neusimbe hwekutamisa (26, 105).Nekuda kweizvozvo, GDE yakarongedzerwa kudzikisa hurombo hwesero kuita nekupa hydrophobic nzira dzinofambisa CO2 kupararira kune catalyst particles (121).GDE yakajairwa inowanzo sanganisira catalyst layer (CL) uye gasi diffusion layer (GDL), sezvinoratidzwa muchikamu chezasi cheFig. 8A (30, 33).Iyo gasi-liquid-catalyst interface yakaumbwa muGDE yakakosha kuvandudza kushanda kwesero.Iyo GDL yakaunganidzwa nezvinhu zvine porous (kazhinji kabhoni bepa) inogona kupa yakawanda CO2 nzira uye ive nechokwadi chekukurumidza kupararira kwe electrolyte.Iyo inoshandawo senge yakaderera-resistance yekufambisa svikiro yemapurotoni, maerekitironi, uye zvigadzirwa zvekudzikisa kubva kuCL kupinda mu electrolyte (121).Drop casting, airbrushing, uye electrodeposition ndiyo yakajairika matekinoroji ekugadzirira maGDEs (122).Macatalysts akaunganidzwa neGDE akaongororwa zvakanyanya muCO2 electroreduction kune C2+ zvigadzirwa.Zvikurukuru, maseru ambotaurwa anoyerera ane mashandiro akanaka ese akasanganiswa nemaGDE.Kare 1990, Sammells nevashandi pamwe navo (123) vakashuma kuti Cu-coated GDEs yakawana yakakwirira FE ye53% ye ethylene ine hupamhi hwepamusoro hwe667 mA cm-2.Kuvandudza kusarudzwa kwe ethylene uye ethanol idambudziko guru rinogara richigadzirwa paCu-based catalysts nekuda kwemaitiro avo akafanana emagetsi maitiro.Uyezve, zvakakosha kuratidza kuti kugadzirwa kwepamusoro uye kusarudzwa kwe ethylene kana ichienzaniswa ne ethanol yakaonekwa paCu-based GDE (25, 36).Gewirth nevashandi pamwe chete (36) vakaratidza FE yakanakisa ye60% ye ethylene uye yakadzvanywa FE ye ethanol ye25% pa electrodeposited Cu-Ag GDE, apo huwandu hwazvino hwasvika ~ 300 mA cm-2 pa -0.7 V kupesana RHE.Iri ibasa risingawanzoiti rakawana sarudzo yakakwira zvakadaro pane yakakura yazvino density.Kuwana uku kunoratidza kuti GDE-yakabatanidzwa electrode inopa inovimbisa nzira yekugadzirisa maitiro ekuita, umo kusarudzwa kwezvakaderedzwa zvigadzirwa zvinogona kuwanikwa pakuwanda kwazvino.

Kugadzikana kweGDE zvakare inyaya yakakosha inofanirwa kugadziriswa nekuti yakagadzikana kushanda kwenguva refu kwakakosha kuti uone kushanda kunoshanda kwemaseru ekuyerera.Pasinei neyakatanhamara CO2-ku-C2 + mashandiro akaitwa neGDEs, kugadzikana kuchiri kushomeka nekuda kwekusasimba kwemagetsi kunamatira kweiyo catalyst, GDL, uye binder layers (77, 124).Iyo kabhoni yepamusoro yeGDL inogona kuchinja kubva kuhydrophobic kuenda kuhydrophilic panguva ye electrochemical reaction nekuda kweiyo oxidation reaction yakaitika pakakwirira overpotentials, izvo zvinotungamira mafashama muGDL uye yakavharira CO2 diffusion nzira (33).Kugadzirisa dambudziko iri, vaongorori vakabatanidza hydrophobic scaffold ye polytetrafluoroethylene (PTFE) muGDEs.Inofananidzwa ne hydrophilic Nafion, hydrophobic PTFE layer inopa kugadzikana kwepamusoro kwenguva refu (33).Sargent uye vashandi pamwe chete (33) vakaunganidza Cu catalyst pakati pePTFE yakaparadzana uye carbon NPs, umo hydrophobic PTFE layer inogona kumisa NPs uye graphite layers, nokudaro kuvaka yakagadzikana electrode interface (Fig. 8, I uye J).Nekuda kweizvozvo, iyo FE yekugadzira ethylene yakawedzera kusvika 70% mu7 M KOH mhinduro pazvino densities ye75 kusvika 100 mA cm-2.Nguva yehupenyu yeiyi inoyerera reactor yakawedzerwa kusvika maawa anopfuura 150 nekurasikirwa kusingakoshi mu ethylene selectivity, iyo yakareba 300-yakareba kupfuura maGDE echinyakare, sezvakaratidzwa muFig. 8K.Sangweji chimiro chakadaro chakaratidzwa kuve chakanakisa GDE dhizaini.Semuyenzaniso, Cui nevashandi pamwe navo (124) vakagadzira trilayer chimiro chine inoshanda electrode layer yakadimburwa nemafirimu maviri ehydrophobic nanoporous polyethylene.Iwo ekunze hydrophobic akaturikidzana anogona kunonotsa kuyerera kwe electrolyte kubva kune yakawanda mhinduro, zvichitungamira kune yakagadzikana, yakakwirira yemunharaunda pH yakatenderedza inoshanda electrode.Kugadziriswa kwenzvimbo ye interlayer, iyo inogona kuvandudza CO2 kutakura uye adsorption, inokoshawo mukugadzirwa kwakadaro (124).Munguva pfupi yapfuura, carbon nanotubes dzakabatanidzwawo muGDEs nekuda kwepamusoro porosity, yakanaka conductivity, uye hydrophobicity, iyo inogona kufambisa electron uye kutakura kwevanhu vakawanda (77).

Pasinei nekufambira mberi kunonakidza paECR, mazano emutengo wakaderera, hukuru-hukuru hweC2 + chigadzirwa hachiwanzovapo (125).Panguva ino, matambudziko nemikana inowirirana kuti unzwisise maitiro eECR uye kutengeserana tekinoroji inovimbisa.

Semhinduro yakanakisa yekuvhara iyo kabhoni loop uye kuchengetedza inopindirana inodzokororwa simba, semhepo uye solar, kufambira mberi kwakakura kwakaitwa kuti uwane shanduko inoshanda yeCO2 mumakumi emakore apfuura.Nepo kunzwisisa kwemaitiro ane chekuita neECR kwasvika kure kubva pamazuva ekutanga (126), iyo C─C yekubatanidza kuburikidza neECR yakanangana neC2 + zvigadzirwa zvichiri kure nekugadzirira kushanda.Muongororo iyi, takatarisa zvakadzama marongero azvino anogona kusimudzira kusarudzwa uye chiyero chekugadzirwa kweC2+ zvigadzirwa kuburikidza neECR, kusanganisira yakanaka-catalyst tuning, electrolyte mhedzisiro, electrochemical mamiriro, uye electrochemical electrode / reactor dhizaini.

Pasinei nekuedza kwese kwakaiswa muECR, kuchine matambudziko mazhinji neazvino zvinokonzeresa uye ECR system inofanirwa kugadziriswa isati yatengeswa ECR.Chekutanga, sechinhu chinotungamira chekuona kubatana kweC─C kunoshanda, Cu inotambura nenyaya dzakakomba dzekugadzikana, kunyanya mumvura ye electrolyte, uye haigone kurarama kwemaawa zana nekuda kwekufamba kwazvo kweatomu, kuunganidzwa kwezvikamu, uye kuparara kwechimiro pasi pemamiriro eECR.Saka, maitiro ekuwana kugadzikana kwenguva refu uchishandisa Cu-based catalyst ichiri dambudziko rakavhurika.Kumisa iyo Cu-based catalyst parutsigiro rwakananga nekudyidzana kwakasimba kungave zano rakavimbika rekuchengetedza iyo catalyst chimiro / morphology uye nekudaro inopa yakawedzera hupenyu hurefu.Uyezve, kushandisa polymer membrane electrolyte kutsiva mvura ine mvura panguva yeECR inogona kuwedzera kuvandudza kugadzikana kweCu-based catalyst.Mukuwedzera, kubva pakuona kwezvinokonzera, in situ / in operando characterization techniques uye theoretical modeling inofanirawo kushandiswa kutarisa uye kunzwisisa iyo catalyst performance decay, nokudaro, kudzvinyirira kuparara uye chepfu yezvinokonzera kusvika kumazinga akaderera.Imwe nyaya yakakosha yeECR catalysts inofanirwa kugadziriswa ndeyekuita kuti synthesis protocol ishande mukugadzirwa kwehuwandu.Kuti izvi zviitike, kukwenenzvera nzira dzekugadzira uchishandisa inowanikwa zvakanyanya feedstocks inosarudzwa.

Chechipiri, iyo C2+ inogadzirwa neokisijeni kubva kuECR inowanzosanganiswa ne solutes (semuenzaniso, KHCO3 uye KOH) mu electrolyte yechinyakare H- kana kuyerera-sero reactors, izvo, zvisinei, zvinoda kumwe kupatsanurwa uye kugadzirisa maitiro kuti udzore yakachena yemafuta emvura mhinduro mukati. zvinoshanda zvikumbiro.Panguva imwecheteyo, iyo yakavepo C2 + hydrocarbons zvakare yakasanganiswa neH2 uye yakasara CO2.Nekudaro, nzira inodhura yekuparadzanisa yakakosha kune yazvino ECR tekinoroji, iyo inowedzera kutadzisa ECR kubva kune inoshanda kushanda.Naizvozvo, maitiro ekuita zvakananga uye nekuenderera mberi nekugadzira yakachena mvura yemafuta mhinduro uye yakachena gasi hydrocarbons, kunyanya ine yakakwira zvigadzirwa, inodiwa zvakanyanya pakutumirwa kunoshanda kweECR.Isu nokudaro tinofanotaura kukosha kwekukwira kwechizvarwa chakananga chezvigadzirwa zvakachena kuburikidza neECR munguva pfupi iri kutevera, izvo zvinogona kutora iyo ECR tekinoroji padyo nemusika (127).

Chechitatu, nepo kuumbwa kweC─O neC─H zvisungo, zvakadai se ethanol, acetic acid, uye ethylene, muECR teknolojia yakanyatsodzidza, kuongorora mamwe marudzi ezvigadzirwa zvakakoshawo kune teknolojia yeECR uye inoratidza kufarira kwehupfumi.Somuenzaniso, munguva pfupi yapfuura, Han uye vashandi pamwe chete (128) vakashuma kugadzirwa kwe2-bromoethnol neECR.Iyo in situ kugadzirwa kweC─Br bond inoshandura chigadzirwa kubva ku ethanol kuenda ku2-bromoethnol, inova yakakosha kuvaka mumakemikari nemishonga synthesis uye inoratidza yakakwirira yakawedzerwa kukosha.Nekudaro, kunze kwezvino zvakadzidzwa zvakanaka zveC2+ zvigadzirwa, isu tinotenda kuti kunangwa kwezvimwe zvisingawanzo ongororwa zvigadzirwa senge oxalic acid (129) uye synthesis yeakanyanya kuomarara maC2+ mamorekuru senge cyclic makomisheni ndeimwe nzira inovimbisa yemangwana ECR tsvagiridzo.

Chekupedzisira asi chisiri chidiki, novel electrode uye reactor dhizaini senge isina mvura GDE, fluid-yekuyerera maseru, uye PEM cell inofanira kugamuchirwa zvakanyanya kuti ikwidze ECR yekugadzira chiyero kusvika padanho rekutengesa (> 200 mA cm-2).Nekudaro, mutsauko mukuru muchiitiko che electrocatalytic unogara uchicherechedzwa kana ma electrocatalysts akaiswa kune yakazara cell test.Naizvozvo, zvimwe zvidzidzo zvakarongeka zvinofanirwa kuitwa kudzikisa mukaha uripo pakati pehafu-sero zvidzidzo uye yakazara-sero mudziyo application kuunza ECR kubva mulab-scale bvunzo kune inoshanda.

Muchidimbu, electrochemical CO2 kuderedza kunopa mukana wakanaka wekuti titarise nyaya yezvakatipoteredza kubva kumagasi ekupisa anobudiswa nemabasa evanhu.Inoratidzawo mukana wekuwana mafuta akachena uye makemikari uchishandisa simba rinodzokororwa.Nepo matambudziko mazhinji achisara eECR tekinoroji padanho razvino, kunyanya yeC─C yekubatanidza maitiro, zvinotendwa kuti nekuenderera mberi nekutsvagisa nekusimudzira pane zvese zvinokonzeresa optimization uye sero kukwana, maonero eiyo chaiyo-nyika CO2 electrolysis yemafuta akachena. uye makemikari achaonekwa munguva pfupi iri kutevera.

Ichi chinyorwa chakavhurika chinogoverwa pasi pemitemo yeCreative Commons Attribution-NonCommercial rezinesi, iyo inobvumidza kushandiswa, kugovera, uye kubereka mune chero svikiro, chero mhedzisiro kushandiswa kusiri kwekutengesa bhizimusi uye kana basa rekutanga rakakodzera. quoted.

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