N'iburu n'uche nchegbu gburugburu ebe obibi na mgbanwe ike, mbelata electrochemical CO2 (ECR) na mmanụ ọkụ multicarbon (C2+) bara uru na kemịkalụ, na-eji ọkụ eletrik emeghari, na-enye ihe ngwọta dị ogologo ogologo oge iji mechie usoro carbon yana uru akụ na ụba agbakwunyere.Agbanyeghị, njikọta C─C electrocatalytic na electrolytes aqueous ka bụ ihe ịma aka mepere emepe n'ihi obere nhọrọ, ọrụ na nkwụsi ike.Nhazi nke ihe na-akpali akpali na reactors na-ejide igodo iji gboo nsogbu ndị ahụ.Anyị na-achịkọta ọganihu n'oge na-adịbeghị anya na otu esi enweta njikọ C─C nke ọma site na ECR, na-emesi ike na atụmatụ dị na electrocatalysts na electrocatalytic electrode/reactor design, na usoro ha kwekọrọ.Na mgbakwunye, a na-atụle mkpọmkpọ ebe ugbu a na ohere ọdịnihu maka ọgbọ ngwaahịa C2 +.Anyị bu n'obi ịnye nleba anya zuru oke nke usoro njikọ C─C nke ọgbara ọhụrụ na obodo maka mmepe na mkpali na nghọta ma ngwa teknụzụ.

Mwepụ nke carbon dioxide gabigara ókè (CO2) n'ime ikuku ebutela nnukwu nsonaazụ gburugburu ebe obibi ma na-ewetakwa ọha mmadụ ihe egwu ngwa ngwa na nke enweghị ike ịgbanwe agbanwe (1, 2).Dika ntinye ikuku CO2 na-abawanye nke oma site na 270 ppm (akụkụ kwa nde) na mbido 1800s rue 401.3 ppm na Julaị 2015, enwetala nkwenye zuru ụwa ọnụ maka ịmegharị akara ukwu carbon nke ọrụ mmadụ na-ewepụta (3, 4).Iji ghọta ihe dị nso maka akara ụkwụ carbon, otu ụzọ nwere ike isi mee bụ ịgbanwe ndabere nke ike dị ugbu a na ụlọ ọrụ kemịkalụ pụọ na mmanụ ọkụ n'ime isi mmalite dị ka anyanwụ na ikuku (5-8).Agbanyeghị, ntakịrị ike sitere na isi mmalite ndị a na-emegharị ọhụrụ bụ naanị 30% n'ihi ọdịdị ha na-adịte aka, ọ gwụla ma ụzọ maka nchekwa nchekwa ike dị ukwuu dị (9).N'ihi ya, dị ka ihe ọzọ, ijide CO2 site na isi mmalite dị ka ụlọ ọrụ ọkụ, na-esote ntughari n'ime nri nri kemịkalụ na mmanụ ọkụ, na-arụ ọrụ nke ọma (9-12).Electrocatalytic CO2 Mbelata (ECR) na-eji ọkụ eletrik emeghari na-anọchite anya ngwọta dị ogologo oge mara mma n'ihi ọnọdụ ọrụ dị nro nke achọrọ maka ntụgharị, nke nwere ike ịhọrọ ngwaahịa ndị nwere uru (13).Dị ka schematically e gosiri na fig. 1, na usoro a, electrochemical electrolyzer na-atụgharị CO2 na mmiri n'ime kemịkalụ na mmanụ ụgbọala kwadoro site na mmeghari ọkụ eletrik.Mmanụ na-esi na ya pụta nwere ike ịchekwa ogologo oge ma nwee ike kesaa ma ọ bụ rie ya, na-enye CO2 dị ka ihe mkpofu bụ isi, nke a ga-ejide ma nyeghachi ya na reactor iji mechie akaghị.Ọzọkwa, enwere ike iji nri nri kemịkalụ obere-molekul (dịka ọmụmaatụ, carbon monoxide (CO) na formate] sitere na ECR dị ka akụrụngwa maka njikọ kemịkalụ gbagwojuru anya.

Enwere ike nweta mmanụ ụgbọala na kemịkalụ site na ECR jiri okirikiri carbon mechiri emechi na-akwado site na isi mmalite ume ọhụrụ dị ka anyanwụ, ikuku, na mmiri.Injinia cell na injinia na-akpali akpali na-arụ ọrụ dị mkpa iji kwalite nhọrọ, ọrụ, na arụmọrụ maka ntụgharị CO2 n'ime ngwaahịa C2 + agbakwunyere bara uru na njupụta ume dị elu.

Agbanyeghị, CO2 bụ molekul kwụ ọtọ kwụsiri ike nke nwere njikọ C═O siri ike (750 kJ mol-1) (14), na-eme ka o sie ike maka ntụgharị elektrọnik.Ya mere, ọ na-achọ ihe mgbochi mgbake dị elu, nke, n'aka nke ya, na-eduga n'ihe ndị dị ịrịba ama (15).Ọzọkwa, ECR na aqueous electrolyte na-agụnye multi-electron/proton usoro mbufe ọnụ na ọnụ ọgụgụ nke dị iche iche mmeghachi omume intermediates na ngwaahịa (16-18), na-eme ka ọ dị mgbagwoju anya.Isiokwu 1 na-achịkọta ọkara electrochemical thermodynamic mmeghachi omume nke isi ngwaahịa ECR, gụnyere CO, methane (CH4), methanol (CH3OH), formic acid (HCOOH), ethylene (C2H4), ethanol (CH3CH2OH), na ndị ọzọ, yana ha. ikike redox ọkọlọtọ kwekọrọ (19).N'ozuzu, n'oge usoro ECR, ụmụ irighiri CO2 na-ebu ụzọ nweta adsorption na mmekọrịta ya na atom n'elu ihe na-eme ka ọ bụrụ * CO2-, na-esote ọkwa dị iche iche nke protons na / ma ọ bụ electrons n'ebe ngwaahịa ikpeazụ dị iche iche.Dịka ọmụmaatụ, a kwenyere na CH4 na-etolite site na ụzọ ndị a: CO2 → *COOH → *CO → *CHO → *CH2O → *CH3O → CH4 + *O → CH4 + *OH → CH4 + H2O (20).

Ọnụ ọgụgụ 2A na-achịkọta arụmọrụ Faradaic (FE) n'okpuru ọnụ ọgụgụ mmepụta dị iche iche (njupụta dị ugbu a) maka ECR electrocatalysts kọrọ, nke na-anọchite anya nhọrọ ngwaahịa nke mmeghachi omume (21-43).N'ụzọ doro anya, ebe ndị na-ahụ maka ndị na-ahụ maka ọkụ eletrik nwere ike gbanwee CO2 n'ime ngwaahịa C1 (CO ma ọ bụ formate) na ihe karịrị 95% FE n'okpuru ọnụ ọgụgụ mmepụta dị elu (> 20 mA cm-2 maka ụdị H-ụdị cell na> 100 mA cm - 2 maka cell eruba) (9, 21, 22, 25, 28, 44, 45), nhọrọ nke ukwuu (> 90%) na mmepụta nke ọma nke kemịkalụ multicarbon (C2+) dị ugbu a emezubeghị.Nke a bụ n'ihi n'eziokwu na ijikọ ngwaahịa C2 + chọrọ mbata na mgbasa ozi nke ọtụtụ mkpụrụ ndụ CO2 n'elu, ngbanwe nke nzọụkwụ, na nhazi ohere (13).Iji kọwaa kpọmkwem, dị ka egosiri na Fig. 2B, mmeghachi omume na-esote * CO intermediates na-ekpebi ngwaahịa C2 + ikpeazụ nke ECR.N'ozuzu, C2H6 na CH3COO- na-ekerịta otu * CH2 etiti, nke a na-emepụta site na proton-coupled eletrọn nzọụkwụ nke * CO.Protonation ọzọ nke * CH2 na-enye * CH3 etiti, nke na-eduga na nguzobe nke C2H6 site na * CH3 dimerization.N'adịghị ka ọgbọ C2H6, CH3COO- bụ site na ntinye CO n'ime * CH2.* CO dimerization bụ nzọụkwụ na-ekpebi ọnụego maka nhazi C2H4, CH3CH2OH, na n-propanol (n-C3H7OH).Mgbe usoro mbufe elektrọn na usoro protonation gasịrị, * CO─CO dimer na-etolite n'etiti * CH2CHO, nke na-eje ozi dị ka usoro nhọrọ nhọrọ maka C2H4 na C2H5OH.Na mgbakwunye, a chọpụtara na ibelata * CH2CHO ka C2H4 nwere ihe mgbochi ike dị ala karịa ịgbanwe * CH3CHO ka C2H5OH (46), nke nwere ike ịkọwa FE dị elu maka C2H4 karịa C2H5OH na ọtụtụ ihe na-eme ọla kọpa.Ọzọkwa, ndị etiti C2 kwụsiri ike nwere ike ibufe na n-C3H7OH site na ntinye CO.Ụzọ mmeghachi omume dị mgbagwoju anya na nke a na-achịkwaghị achịkwa n'oge a na-emepụta kemịkalụ C2+ bụ n'ihi ọtụtụ ihe ndị ọzọ na-emegharị na saịtị protonation, yana itinye aka na nzọụkwụ nonelectrochemical (19, 47).Dị ka nke a, imewe nke electrocatalysts nke ukwuu bụ ihe dị mkpa maka ịmepụta ngwaahịa C2 + kpọmkwem na mkpụrụ dị elu.Na nyocha a, anyị bu n'obi ịkọwapụta ọganihu na-adịbeghị anya na atụmatụ na nhazi electrocatalyst maka ịhọrọ ngwaahịa C2 + site na ECR.Anyị na-enyekwa nchịkọta nke nghọta nke usoro ndị metụtara ya.A ga-emesikwa ike imewe electrode na reactor iji gosi otu esi arụ ọrụ nke ọma, kwụsie ike, yana nnukwu ọrụ ECR.Ọzọkwa, anyị ga-atụle ihe ịma aka ndị fọdụrụ na ohere ọdịnihu maka ntụgharị electrochemical nke CO2 n'ime kemịkalụ C2+ bara uru.

(A) FE n'okpuru ọnụego mmepụta dị iche iche (njupụta dị ugbu a) maka ECR electrocatalysts kọrọ (21-43, 130).(B) Ụzọ C2+ kacha kwe omume n'oge ECR.Emegharịrị site na ikike sitere na American Chemical Society (47).

Mgbanwe Electrocatalytic nke CO2 n'ime mmanụ ọkụ kemịkalụ na nri nri bụ teknụzụ nwere ike iji nweta okirikiri ike carbon-anọpụ iche (11).Otú ọ dị, FE nke ngwaahịa C2 + ka dị anya site na ngwa bara uru, ebe ndị na-emepụta ihe na-emepụta ihe na-enye ohere ịmepụta ngwaahịa C2 na gburugburu 60% FE (13, 33), ebe mmepụta C3 na-ejedebe na-erughị 10% FE (48, 49).Njikọ mbelata nke ngwaahịa CO2 gaa na C2+ chọrọ ihe mkpali dị iche iche nwere akụrụngwa morphological na eletrọnịkị nwere ahaziri nke ukwuu (50, 51).Elu catalytic kwesịrị imebi mmekọrịta dị n'etiti etiti (47, 52, 53).Ọzọkwa, iji nweta nguzobe nke C─C, mmeghachi omume na-etinye obi n'etiti etiti n'elu ihe na-akpata ga-adịrịrị nso n'ebe ibe ya nọ.Ọzọkwa, ụzọ sitere na etiti etiti agbadoro na mbụ gaa n'otu ngwaahịa C2+ kwesịrị ka achịkwa nke ọma n'ihi usoro mbufe elektrọn na-enyere ọtụtụ proton aka.N'ịtụle nnukwu mgbagwoju anya nke CO2 mbelata na ngwaahịa C2 +, ekwesịrị iji nlezianya hazie ndị electrocatalysts iji mee ka nhọrọ ahụ dịkwuo elu.Dabere na ụdị etiti na ihe mejupụtara kemịkalụ, anyị na-ekewa ngwaahịa C2+ n'ime multicarbon hydrocarbons na oxygenates (4, 54).Iji bịaruo nso electrocatalysts na-arụ ọrụ nke ọma maka mmepụta mkpụrụ ndụ C2 + kpọmkwem, egosipụtara ọtụtụ atụmatụ imewe ihe, dị ka heteroatom doping, kristal facet regulation, alloy/dealloying, oxidation state tuning, and surface ligand control, egosila (35, 41, 55-61). .Nhazi kacha mma kwesịrị iji ezi uche tụlee mmetụta ndị ahụ e kwuru n'elu wee bulie uru ya.Ma ọ bụghị ya, ịghọta ihe ebumnobi saịtị na-eduga n'ụdị omume catalytic pụrụ iche nwere ike na-amụbawanye ìhè na nhazi ihe nrụpụta maka njikọta C─C.N'ihi ya, a ga-atụle otu esi emepụta ECR catalyst n'ebe ngwaahịa dị iche iche (multicarbon hydrocarbons na oxygenates) na usoro yiri ya n'akụkụ a.

C2+ hydrocarbons, dị ka C2H4, bụ kemịkalụ nexus maka ụdị ọrụ kemịkal dị iche iche, dị ka mmepụta polyethylene (62, 63).E wezụga nke ahụ, a pụrụ iji ya mee ihe ozugbo dị ka mmanụ ọkụ maka ịgbado ọkụ ma ọ bụ ihe ngwakọta na gas (12).Hydrogenation nke CO (Fischer-Tropsch synthesis) na CO2 ejiriwo na-emepụta C2 + hydrocarbons ruo ogologo oge na ụlọ ọrụ mmepụta ihe ma na-agbagha site na nnukwu ike oriri na mmetụta gburugburu ebe obibi (64).N'ụzọ dị nnọọ iche, mbelata electrochemical CO2 site na iji ume ọhụrụ na-enye ụzọ dị ọcha na nke ga-adigide.E meela nnukwu mbọ iji mepụta ihe ọkụ eletrik na-arụ ọrụ nke ọma na C2+ hydrocarbons (32, 33, 65-70).

A na-enyochakarị electrocatalysts Bimetallic iji mebie mmekọrịta na-ekpo ọkụ n'oge mgbanwe electrochemical CO2, nke nwere ike ime ka etiti etiti dị n'etiti ma belata ike na-enweghị ike ma, ya mere, n'aka nke ya, na-abawanye nhọrọ (71-74).Ọ bụ ezie na egosipụtara ọtụtụ ihe alloy gụnyere Au-Cu, Ag-Cu, Au-Pd, na Cu-Pt maka mmepụta C1 dị elu site na ime ka etiti dị oke egwu (73, 75), mmetụta alloy na nhazi C2+ hydrocarbon yiri ka. ịdị mgbagwoju anya (76).Dịka ọmụmaatụ, na usoro Cu-Ag bimetallic, enwere ike ịchịkwa nkesa ngwaahịa ahụ n'ụzọ dị mfe site n'ịkwado oke atọm nke Ag na Cu (77).A na-ahọrọ ihe nlele elu Cu-ọgaranya maka mmepụta hydrocarbon, ebe ngwaahịa nke elu Ag-ọgaranya na-achịkwa CO, na-egosipụta mkpa ọ dị na nha atọ maka alloyed ECR electrocatalysts.Mmetụta geometric nke nhazi atomiki mpaghara kpatara nwere ike imetụta ike njide nke etiti.Gewirth na ndị ọrụ na-arụkọ ọrụ (36) gosiri na Cu-Ag alloys si na mgbakwunye na-achịkwa electrodeposition gosipụtara ~ 60% FE maka C2H4 na alkaline eruba electrolyzer (Fig 3, A na B).N'okwu a, enwere ike nweta nhọrọ C2H4 kachasị mma site na morphology na ngbanwe Ag-loading.Ekwenyere na saịtị Ag na-arụ ọrụ nke onye nkwalite maka nguzobe CO n'oge ECR.Mgbe ahụ, nnweta kacha mma nke etiti CO nwere ike inyere njikọ C─C aka na Cu agbataobi.E wezụga nke ahụ, Ag nwekwara ike ịkwalite nhazi nke Cu2O n'oge Cu-Ag catalyst synthesis (Fig 3C), na-eme ka mmepụta C2H4 dịkwuo mma.Mmekọrịta a na-emepe ohere ọhụrụ maka ịmepụta ihe na-akpata njikọ C─C.Ọzọkwa, usoro ngwakọta nke ọla dị iche iche na sistemụ alloy nwekwara ike ikpebi nkesa ngwaahịa ECR.N'iji Pd-Cu alloy dị ka ihe atụ (Fig 3D), Kenis na ndị ọrụ (71) gosipụtara na Pd-Cu catalyst nke na-ekewapụ oge nwere ike inye nhọrọ kachasị elu (~ 50%) maka C2H4 ma e jiri ya tụnyere ya nyere iwu na nsogbu. ogbo.Dị ka echiche d-band siri dị, ọ na-adịkarị, igwe ngbanwe nwere etiti d-band dị ala na-egosi njikọ na-esighị ike nke ebe a na-emepụta etiti n'elu igwe (78).Ọ bụ ezie na Pd-Cu alloy kewapụrụ agba na-egosipụta ụdị catalytic selectivity na ọrụ maka CO na Cu nanoparticles (NPs), ọ na-enye ike njide dị iche iche na etiti site na ntugharị Pd.Dị ka e gosiri na fig. 3E, akụkụ-kewapụrụ Cu-Pd alloy gosiri kasị ala-agha ụgha d-band center, ebe nke Cu NP bụ kasị elu.Ọ na-atụ aro na Cu-Pd alloy kewapụrụ agba nwere ike njide kacha ala maka etiti CO.Nlebanya a na-egosi na mmetụta geometric na nhazi nwere ike ịrụ ọrụ ka ukwuu karịa mmetụta eletrọnịkị maka imeziwanye nhọrọ nke hydrocarbon n'ime akpa kewara Cu-Pd alloy case.Ka ọ dị ugbu a, naanị ọla kọpa dị ọcha ma ọ bụ ọla kọpa dabere na-egosi nhọrọ dị elu na ọrụ maka mbelata electrochemical nke CO2 ruo C2+ hydrocarbons.Ya mere, ọ dị ezigbo mkpa ịmepụta electrocatalyst akwụkwọ akụkọ maka mmepụta C2 + hydrocarbon sitere na ECR.N'ịbụ onye sitere na CO2 hydrogenation, nchọpụta mmalite gosipụtara na Ni-Ga alloy nwere usoro dị iche iche nwere ike iji maka ọgbọ C2H4 (79).O gosiri na ihe nkiri Ni5Ga3 nwere ike ibelata CO2 na C2H4 na ethane (C2H6).Ọ bụ ezie na FE na C2 + hydrocarbons dị ihe na-erughị 5%, ọ nwere ike imepe ahịrị ọhụrụ maka nyocha electrocatalyst na njikọ C─C dabere na mmetụta alloy.

(A ruo C) Cu-Ag bimetallic catalysts ekepụtara site na mgbakwunye electrodeposition na-achịkwa: (A) nyocha eletrọnịkị microscopy (SEM) nke Cu waya, Cu-Ag poly, na Cu-Ag waya na (B) kwekọrọ C2H4 FE.(C) EXAFS gosiri na a gwakọtara waya Cu-Ag n'otu aka ahụ yana Cu (I) oxide gosipụtara.(A) ruo (C) ka emegharịrị site na ikike sitere na American Chemical Society (36).(D na E) Cu-Pd na-eme ka ndị nwere usoro ngwakọta dị iche iche: (D) Ihe atụ, ihe onyonyo na-ebugharị eletrọnịkị (TEM), na maapụ spectroscopy nke ike na-agbasa nke nyere iwu, enweghị nsogbu, na nkewapụ Cu-Pd alloys na (E) ) elu valence band photoemission spectra na d-band center (ahịrị kwụ ọtọ) nke Cu-Pd alloys metụtara ọkwa Fermi.(D) na (E) ka emegharịrị site na ikike sitere na American Chemical Society (71).au, nkeji aka ike.

E wezụga mmetụta alloy, ịmegharị steeti oxidation bụ ụkpụrụ ọzọ dị mkpa iji mee ka arụmọrụ nke electrocatalysts dị mma, nke nwere ike imetụta usoro elektrọnik mpaghara nke ihe ahụ.Ihe atụ mbụ maka nlegharị anya steeti oxidation nke ihe na-akpata bụ iji ihe ndị sitere na oxide.Ụdị ikuku oxygen fọdụrụnụ n'elu ma ọ bụ n'okpuru ala nke ihe na-eme ka ọ bụrụ mbelata ọnọdụ nwere ike ịhazi ọnọdụ oxidation nke etiti igwe.Dịka ọmụmaatụ, plasma-oxidized Cu gosipụtara ihe karịrị 60% nhọrọ n'ebe C2H4 nọ, bụ nke e nyere na Cu+ na-eguzogide mbelata (37).Iji gosi na Cu + bụ isi ihe dị mkpa maka elu ethylene selectivity, anyị mere nyocha njikwa site na iji plasma dị iche iche (Fig 4A).N'ebe ahụ siri ike x-ray absorption spectroscopy gosikwara na ihe ndị fọdụrụ na oxides dị na oyi akwa (sub) dị elu kwụsiri ike megide ọnọdụ mbelata, yana ọnụ ọgụgụ dị ukwuu nke ụdị Cu+ fọdụrụ mgbe 1 hour nke mbelata na ikike dị elu nke -1.2 V na-agbanwe agbanwe. hydrogen electrode (RHE).Ọzọkwa, electroredeposition nke ọla kọpa si sol-gel ọla kọpa oxychloride kwenye ọzọ na kwụsiri ike n'elu Cu + ụdị nwere ike imeziwanye selectivity nke C2H4 (61).A na-enyocha ọnọdụ oxidation nke ihe na-akpata ọla kọpa n'okpuru ikike dị iche iche etinyere n'ọrụ site na iji oge edoziri n'ọnọdụ ọnọdụ mmịpụta x-ray dị nro.Nzọụkwụ mbụ site na Cu2+ gaa na Cu+ dị ngwa ngwa;Otú ọ dị, mbelata electrochemical ọzọ nke ụdị Cu+ na Cu0 na-eji nwayọọ nwayọọ.Ihe dị ka 23% nke ụdị Cu + na-anọgide ọbụna mgbe 1-hour mbelata mgbe niile n'okpuru -1.2 V megide RHE (Fig. 4B).Ihe omumu ihe omumu gosiputara na uzo di n'etiti Cu + na Cu0 na-eduga na mmasi electrostatic n'etiti ndi etiti ebe C atom nke * CO @Cu + bu nke oma, ebe nke * CO@Cu0 bu ebubo ojoo (80), nke, n'aka nke ya, na-akwalite Nhazi nke C─C ma si otú a na-emepụta C2+ hydrocarbons.Na mgbakwunye na ihe ndị sitere na oxide, a na-ejikwa ọla kọpa nitride (Cu3N) nweta ụdị (sub) dị n'elu Cu+ iji belata ihe mgbochi ike nke * CO (81).Na mgbakwunye, ma e jiri ya tụnyere oxide-ewepụtara Cu, ụdị Cu + sitere na Cu3N na-akwụsi ike karịa (Fig 4C).N'ihi ya, ihe na-emepụta ọla kọpa nke nitride na-egosipụta FE nke 39 ± 2% maka C2H4, na-eme ka Cu (~ 23%) dị ọcha na oxide-derived Cu (~ 28%).Dị ka usoro Cu+/C a kpọtụrụ aha n'elu, boron ka ejirila heteroatom dopant webata ma kwụsie ike Cuδ+ (41).Enwere ike ịchịkwa nkezi oxidation steeti ọla kọpa site na +0.25 ruo +0.78 site n'ịgbanwe mkpokọta boron dopant.Njupụta nke steeti gosiri na eletrọn na-ebufe site na ọla kọpa gaa boron, na-eduga na saịtị ọla kọpa nke dopant butere nke ọma.Ọla kọpa boron-doped gosipụtara ike nrụpụta nke * CHO etiti na, yabụ, kwụsịrị ụzọ mmeghachi omume na ngwaahịa C1.Na mgbakwunye, ọ nwere ike ịbawanye nhọrọ n'ihu multicarbon hydrocarbons site na ibelata * CO dimerization mmeghachi omume ume (Fig. 4D).Site na-emeziwanye ọnọdụ oxidation elu nke ọla kọpa, nnukwu C2 FE nke ~ 80% na ~ 53% C2H4 nwere ike nweta n'okpuru ọnọdụ oxidation ọla kọpa + 0.35 (Fig. 4E).Ka ọ dị ugbu a, a chọpụtala saịtị ndị na-arụ ọrụ na ọla kọpa dị ka Cu0, Cuδ +, na/ma ọ bụ interface ha maka ECR na ọmụmụ dị iche iche (39, 41, 42, 81, 82).Otú ọ dị, a ka na-arụrịta ụka ihe bụ saịtị na-arụ ọrụ.Ọ bụ ezie na egosipụtara na heteroatom doping-induced Cuδ + catalysts ka ọ na-arụsi ọrụ ike maka ECR n'ebe ngwaahịa C2+ nọ, a ga-atụlekwa mmetụta synergistic sitere na ntụpọ na oghere ndị a na-emepụta n'otu oge.N'ihi ya, ekwesịrị ịmepụta usoro nhazi na njirimara operando iji chọpụta ebe etiti na-arụ ọrụ n'elu ọla kọpa ma nyochaa ike na mgbanwe ọnọdụ nke saịtị ndị na-arụ ọrụ n'okpuru ọnọdụ mmeghachi omume.E wezụga nke ahụ, nkwụsi ike nke ọla kọpa a kwadoro nke ọma bụ nchegbu ọzọ n'okpuru ọnọdụ mbelata electrochemical.Otu esi eji saịtị Cuδ+ arụkọ ọrụ katalis ka bụ ihe ịma aka.

(A) Nchịkọta nke C2H4 selectivity dị iche iche na-eme ka ọla kọpa rụọ ọrụ plasma.Mepụtaghachi ya site na ikike sitere na Otu Nbipụta Nature (37).Ogwe ọnụ ọgụgụ, 500 nm.(B) Ratio nke Cu oxidation na-ekwu maka oge mmeghachi omume na -1.2 V megide RHE na ọla kọpa eletrọd.Mepụtaghachi ya site na ikike sitere na Otu Nature Publishing Group (61).(C) Ratio nke ụdị Cu + nwere ọrụ nke oge mmeghachi omume na -0.95 V megide RHE na Cu-on-Cu3N ma ọ bụ Cu-on-Cu2O.Mepụtaghachi ya site na ikike sitere na Nature Publishing Group (81).(D) Boron doping nwere ike ịgbanwe nkezi adsorption ike nke CO n'elu ọla kọpa wee belata CO─CO dimerization ume.1[B], 2[B], 3[B], 4[B], na 8[B] na-ezo aka na mkpokọta boron doping nke dị n'okpuru ihe na-eme ka ọla kọpa, bụ 1/16, 1/8, 3/ 16, 1/4, na 1/2, n'otu n'otu.(E) Mmekọrịta dị n'etiti steeti oxidation na FE nke ngwaahịa C2 ma ọ bụ C1 na boron-doped ọla kọpa.(D) na (E) ka emegharịrị site na ikike sitere na Otu Nbipụta Nature (41).(F) Ihe onyonyo SEM nke foils ọla kọpa nwere ọkpụrụkpụ dị iche iche nke ihe nkiri Cu2O tupu (elu) na mgbe (ala) ECR.Emegharịrị site na ikike sitere na American Chemical Society (83).

Ewezuga ihe owuwu eletrọnịkị, ihe ndị sitere na oxide nwekwara ike iduga n'ọdịdị ọdịdị ma ọ bụ nhazi usoro n'oge usoro mbelata ọnọdụ.Site n'echiche nke morphology ma ọ bụ nhazi, arụ ọrụ electrochemical emelitere nke electrocatalysts sitere na oxide ka ekwuru na nhazi nke oke ọka na-arụ ọrụ, akụkụ, na nzọụkwụ (83-85).Yeo na ndị ọrụ ibe (83) kọrọ nchịkọta C─C nhọrọ na ihe nkiri Cu2O electrodeposited na ọkpụrụkpụ dị iche iche (Fig 4F).N'ime ọnọdụ Raman spectroscopy kpughere na elu nke ihe nkiri Cu2O belatara ka ọ bụrụ nnukwu ọla Cu0 n'oge ECR (83).N'ihi ya, a kwadoro Cu0 dara dị ka ebe na-arụ ọrụ catalytic kama ụdị Cu+ ma ọ bụ interface Cu+/Cu0.N'ime usoro ibelata Cu2O ka ọ bụrụ nke dara Cu0, elu ihe na-eme ka ọ dị n'ọnọdụ ọ ga-abụ steepụ, akụkụ, na mbara ala.E gosiputara na steepụ na akụkụ ndị a kpụrụ akpụ na-arụsi ọrụ ike karịa mbara ala, sitere na njikọ siri ike ha na * CO, nke nwere ike ịga n'ihu hydrogenate * CO na * CHO ma ọ bụ * CH2O.E wezụga nke ahụ, atom Cu bụ onye na-akwalite ịkwalite * CHO na * CH2O nhazi.Ọrụ gara aga tụrụ aro na * CHO na * CH2O etiti dị mma maka njikọta C─C karịa * CO na kinetics (86).Site n'ịhazi ọdịdị ọdịdị elu, enwere ike ịkwalite ike chemisorption nke * CHO na * CH2O intermediates.N'ime ọmụmụ ihe a, ndị edemede chọpụtara na FE nke C2H4 belatara site na 40 ruo 22% mgbe ha mụbara ọkpụrụkpụ nke ihe nkiri Cu2O dị mkpa site na 0.9 ruo 8.8 μm.Nke a bụ n'ihi ntinye nke Cu chịkọbara dị ala nke na-abawanye site na mmụba na ọkpụrụkpụ Cu2O.Atọm ndị a na-ejikọtaghị ọnụ nwere ike jikọta ya na H na, yabụ, a na-ahọrọ maka evolushọn hydrogen karịa njikọ C─C.Ọrụ a gosipụtara na ihe na-eme ka ọla kọpa na-enweta oxide nwere ike ime ka nhọrọ C2H4 dịkwuo mma site na nrụgharị morphology elu kama iwebata ụdị Cuδ + ebubo.N'iji ihe na-eme ka oxide nweta, ethane (C2H6) ka emeputakwara nke ọma site n'enyemaka nke palladium (II) chloride (PdCl2) mgbakwunye na electrolyte (34).Ọ gosipụtara na PdClx adsorbed n'elu Cu2O-ewepụtara Cu rụrụ ọrụ dị mkpa maka evolushọn C2H6.Kpọmkwem, CO2 bu ụzọ belata ka ọ bụrụ C2H4 na saịtị Cu2O enwetara arụ ọrụ, wee bụrụ C2H4 etolite ga-abụ hydrogenated site na enyemaka nke PdClx adsorbed iji mepụta C2H6.FE nke C2H6 mụbara site na <1 ruo 30.1% site n'enyemaka nke PdCl2.Ọrụ a na-egosi na nchikota nke ECR nke ọma na mgbakwunye electrolyte nwere ike imeghe ohere ọhụrụ maka mmepụta ngwaahịa C2 + kpọmkwem.

Usoro ọmụmụ na/ma ọ bụ ụkpụrụ nhazi na-anọchi anya atụmatụ ọzọ iji gbanwee nhọrọ na ọrụ catalytic.Ịchịkwa nha, ọdịdị, na akụkụ ekpughere nke ihe na-akpata egosipụtara n'ọtụtụ ebe maka nkwalite arụmọrụ ECR (58, 87, 88).Dịka ọmụmaatụ, ihu Cu (100) na-amasịkarị maka ọgbọ C2H4, ebe ngwaahịa a na-achịkwa sitere na Cu (111) catalyst bụ methane (CH4) (87).N'ime ọmụmụ nke Cu nanocrystals nwere ụdị na nha dị iche iche, Buonsanti na ndị na-arụkọ ọrụ (58) kpughere ịdabere na nha nke na-abụghị mononotonic nke C2H4 selectivity na nanocrystal ọla kọpa nwere ụdị cube (Fig 5A).N'ime ime, cubic Cu nanocrystals gosipụtara ọrụ C2H4 dị elu yana nhọrọ nhọrọ karịa Cu nanocrystals dị okirikiri n'ihi oke nke akụkụ (100).Nha kristal dị ntakịrị nke cubic Cu nwere ike inye ọrụ dị elu n'ihi mmụba nke saịtị elu ndị a na-ahazi nke ọma, dị ka akụkụ, steepụ, na kinks.Otú ọ dị, chemisorption siri ike nke saịtị ndị dị ala na-ejikọta ya na H2 dị elu na nhọrọ CO, na-eme ka hydrocarbon FE dị ala.N'aka nke ọzọ, oke nke saịtị ihu na saịtị ụgbọ elu belatara na mmụba nke nha nha, nke na-emetụtakwa arụmọrụ nke mmepụta C2H4.Ndị ode akwụkwọ gosipụtara na nanocubes ọla kọpa nke etiti nwere ogologo akụkụ 44-nm gosipụtara nhọrọ C2H4 kachasị elu n'ihi nguzozi kachasị n'etiti nha nha na njupụta nke saịtị ihu.Ọzọkwa, morphology nwekwara ike imetụta pH mpaghara na njem njem n'oge ECR.Egosiputara na pH dị elu dị n'akụkụ ebe ihe na-eme ka ọ dị elu, nke sitere na ebe a na-emepụta OH-, na-egbochi ụzọ mmeghachi omume proton na-etinye aka.N'ihi nke a, enwere ike ịkwalite mmepụta C2+ hydrocarbon site na * CO dimerization, yana CH4 kpụrụ site na * COH etiti nwere ike igbochi.Egosiputara usoro nanowire ọla kọpa (Fig 5B) iji nweta ụbara pH mpaghara (68).Dị ka electrolyte a na-ejikarị eme ihe, CO2 saturated potassium bicarbonate (KHCO3) ngwọta ga-ewepụ ngwa ngwa OH- (HCO3- + OH- = CO32- + H2O) ma belata pH mpaghara.Site na microstructure elongated, mgbasa nke HCO3- n'ime usoro Cu nanowire nwere ike mebie n'ụzọ ụfọdụ ka a ga-ebelata mmetụta nkwụsịtụ maka OH-obodo ruo n'ókè ụfọdụ.Na ndabere nke ụkpụrụ yiri nke a, ọla kọpa meshes na mesopores na-achịkwa nke ọma (Fig 5C) gosipụtara nkwalite FE maka mmepụta C2H4 ma ọ bụ C2H6 (32).O gosipụtara na pH mpaghara dị na elu electrode nwere ike ịbawanye site na ibelata obosara pore, na-eme ka C1 ngwaahịa FE belata ma kwalite C2 ngwaahịa FE.E wezụga nke ahụ, site n'ịbawanye omimi nke pore, enwere ike ịmegharị ngwaahịa mbelata isi site na C2H4 ruo C2H6.FE nke C2H6 dị elu dịka 46%.Ebe ọ bụ na ekpochila kemịkalụ n'ime pores n'oge ECR, a kọwawo ogologo oge njigide nke isi etiti nke oghere dị omimi kpatara dị ka isi ihe kpatara nhọrọ dị elu na C2 hydrocarbon jupụtara.Cu nanofibers sitere na CuI gosikwara oke nhọrọ na C2H6 (FE = 30% na -0.735 V vesos RHE) (89).Usoro anisotropic morphology na elu elu elu nke Cu nanofibers sitere na CuI nwere ike melite arụmọrụ ọnyà nke etinye uche H2 ma si otú ahụ mụbaa FE nke C2H6.

(A ruo C) Mkpesa ọmụmụ ma ọ bụ nhazi usoro.(A) Njupụta nke atọm (axis aka ekpe) na nha nke atọm na saịtị nsọtụ (Ndge) na atọm na ụgbọ elu (100) (N100) (axis aka nri) na mkpa na ogologo nsọtụ (d).Emegharịrị site na ikike sitere n'aka John Wiley na Sons (58).(B) Atụmatụ morphology mere ka pH gbanwee.Emegharịrị site na ikike sitere n'aka John Wiley na Sons (68).(C) Nhọrọ ngwaahịa nke ọla kọpa mesopore nwere nha nha na omimi dị iche iche.Emegharịrị site na ikike sitere n'aka John Wiley na Sons (32).(D ruo H) mmetụta Ligand.(D na E) ECR na ọla kọpa nanowire (Cu NW) nwere ụdị amino asịd dị iche iche (D) ma ọ bụ ndị mgbanwe (E) na -1.9 V. Megharịrị site na ikike sitere na Royal Society of Chemistry (35).(F) Ọnụego mmepụta nke C2H4 na electrolytes halide dị iche iche nwere ikike mgbasa ozi dị iche iche na Cu (35).Emegharịrị site na ikike sitere na American Chemical Society (91).NHE, nkịtị hydrogen electrode.(G) FE nke C2H4 na CO dị iche iche nke KOH electrolytes na (H) Tafel mkpọda nke C2H4 dị iche iche nke KOH electrolytes.(G) na (H) na-ebipụta site na American Association for the Advancement of Science (AAAS) (33).

Mgbanwe elu nke ihe na-eme ka ọ bụrụ obere ụmụ irighiri ihe bụ atụmatụ ọzọ a ma ama iji melite arụmọrụ electrochemical nke ECR.Usoro a nwere ike imetụta microenvironment dị nso na elu nke na-eme ka ọ dị elu, nke nwere ike ịkwado ndị isi etiti n'ihi mmekọrịta dị n'etiti ligand elu na etiti.A kọwala Amine dị ka ihe mgbanwe iji kwalite ECR (35).Achọpụtala amino acid dị iche iche, gụnyere glycine (Gly), dl-alanine (Ala), dl-leucine (Leu), dl-tryptophan (Tyr), dl-arginine (Arg), na dl-tryptophan (Trp), na mụọ mmetụta ha na ọla kọpa nanowires (35).Dị ka egosiri na fig.5D, njikọ amino acid niile nwere ike imeziwanye nhọrọ nke C2+ hydrocarbons.Nkwalite dị otú ahụ na-egosi na ─COOH na ─NH2 na-arụ ọrụ dị na amino acid nwere ike na-ahụ maka nkwalite nhọrọ nke ECR.Akụkọ ndị gara aga gosiri na a na-enweta nnabata nke amino acid n'elu Cu site na otu ─COOH na ─NH2 (35, 90).Stearic acid (C17H35COOH, RCO2H), nke nwere naanị otu ─COOH, ka ahọpụtara iji mata ọrụ nke ─COOH.Ndị ọzọ na-agbanwe agbanwe, dị ka a-anthraquinone diazonium salt (AQ), o-nitrobenzene diazonium salt (PhNO2), na dodecyl mercaptan (C12H25SH, RSH), nke na-enweghị ─COOH ma ọ bụ ─NH2 otu, ka enyochakwara.Agbanyeghị, ha niile adịchaghị mma maka nkwalite C2 + hydrocarbon FE (Fig 5E).Ngụkọta usoro ihe ọmụmụ gosiri na ─NH3+ dị na adsorbed zwitterionic glycine nwere ike kwụsie ike * CHO etiti n'ihi mmekọrịta siri ike ha, dị ka njikọ hydrogen.Mmalite nke ion halide n'ime electrolyte bụ ụzọ ọzọ isi gbanwee ihe ndị na-akpali akpali (91, 92).Dị ka egosiri na fig. 5F, ọnụego mmepụta C2H4 na plasma-arụ ọrụ Cu nwere ike ịbawanye nke ọma site n'enyemaka nke ihe mgbakwunye halide.E gosipụtara na I-ion na-arụsi ọrụ ike karịa Br- na Cl-, na nkwekọrịta na ike mgbasa ozi kwekọrọ ekwekọ nke I-, Br-, na Cl- na Cu (100) facet (91).E wezụga halides, ion hydroxide gosikwara mmetụta dị mma na nhọrọ C2H4.N'oge na-adịbeghị anya, Sargent na ndị ọrụ (33) kọrọ mgbanwe CO2-to-C2H4 na ~ 70% FE site na iji potassium hydroxide (KOH) electrolyte concentrated (ruo 10 M) na cell na-asọpụta.Dị ka e gosiri na fig. 5G, ikike mmalite nke CO na C2H4 na 10 M KOH electrolyte dị ala karịa nke ahụ na 1 M KOH.Ọzọkwa, mkpọda Tafel (Fig 5H) nke nhazi C2H4 belatara na mmụba nke mkpokọta hydroxide (135 mV afọ iri-1 na 1 M KOH na 65 mV afọ iri-1 na 10 M KOH), na-atụ aro ka ntụgharị nke mkpokọta ọnụego- na-ekpebi nzọụkwụ.Nchọpụta arụrụ arụ ọrụ nke density (DFT) gosipụtara na ọnụnọ nke hydroxides gbanyere mkpọrọgwụ nwere ike belata ike njikọ nke CO intermediate ma mee ka enweghị ahaghị nhata n'etiti carbon carbon abụọ na etiti OCCO adsorbed.N'ihi nke a, a ga-eme ka etiti OCCO guzosie ike site na mmasị dipole siri ike, na-eduga n'ibelata ihe mgbochi ike ike maka dimerization CO, nke ga-emeziwanye arụmọrụ n'ozuzu ya.

C2+ oxygenates dị ka ethanol (CH3CH2OH) bụ akụkụ ọzọ bụ isi nke ngwaahịa ECR bara uru nke ukwuu.Ngwakọta ụlọ ọrụ nke ethanol bụ usoro na-arụ ọrụ ike, nke na-erikwa nnukwu ethylene ma ọ bụ nri nri ugbo (40).Ya mere, mmepụta electrocatalytic nke ethanol ma ọ bụ C2 + oxygenates sitere na CO2 na-eme ka ọtụtụ echiche akụ na ụba na gburugburu ebe obibi.Ebe ọ bụ na ọgbọ ethanol sitere na ECR na-ekerịta C2H4 nke bụ * C2H3O (43), hydrogenation nhọrọ nke etiti a nwere ike ịgbanwe ụzọ ECR site na C2H4 gaa na mmanya (64).Otú ọ dị, n'ọtụtụ usoro, nhọrọ na C2 + oxygenates dị ala karịa hydrocarbons (31, 37, 39, 41, 42, 67).Ya mere, na ngalaba a, anyị ga-akọwapụta atụmatụ nhazi electrocatalyst nke nwere ike nweta nnukwu C2 + oxygenate FE nke karịrị 25%.

Dị ka a tụlere n'elu, ndị na-emepụta bimetallic a haziri nke ọma nwere ike imezi nhọrọ na ọrụ maka mmepụta C2+ hydrocarbon.A na-ejikwa usoro yiri nke ahụ ma ọ bụghị otu ya iji melite arụmọrụ electrocatalytic maka C2+ oxygenates (38, 93, 94).Dị ka ọmụmaatụ, Ag-incorporated Cu-Cu2O catalysts gosipụtara tunable ethanol selectivity, na ethanol FE kachasị elu bụ 34.15% (95).Oke biphasic dị n'ụdị agwakọta Ag-Cu alloy, kama ag/C atomic ratio, bụ isi ihe na-eme ka mmepụta ethanol họrọ.Ebe ọ bụ na saịtị Cu dị nso na saịtị Ag na usoro jikọtara ọnụ (Ag-Cu2OPB), ọnụ ọgụgụ nhazi nke ethanol intermediates maka ihe atụ-ejikọta ọnụ nwere ike ịkwalite ma e jiri ya tụnyere nke nkewapụrụ (Ag-Cu2OPS). ), na-eduga na arụmọrụ ọgbọ ethanol ka mma.E wezụga ethanol, egosipụtawokwa Cu-Ag bimetallic NP iji gbanwee CO2 ka ọ bụrụ acetate na mgbakwunye nke benzotriazole (93).Na -1.33 V na RHE, FE nke acetate bụ 21.2%.Atụpụtara ụzọ mmeghachi omume abụọ nwere ike ime na nke a: Otu dabere na CO dimerization, nke ọzọ bụ na ntinye CO, na-egosipụta ọrụ dị oke mkpa nke nhazi etiti CO na saịtị Ag na-arụ ọrụ.A kọwapụtara ihe nlele yiri ya na Cu-Zn catalysts (Fig 6, A na B) maka mmepụta ethanol (38).Site na imezi ọdịnaya nke Zn na Zn-Cu alloyed catalysts, oke nke ethanol megide C2H4 FE nwere ike ịchịkwa nke ọma na oke 0.48 ruo 6, na-atụ aro mkpa saịtị na-agbanwe CO maka C2+ oxygenate guzobere.Ịmepụta ihe ndị na-eme ka alloyed nwere ike ịkpata mmetụta dị n'ahụ matriks ahụ, nke nwere ike ọ gaghị achọ mgbe ụfọdụ.Ya mere, ụzọ a kapịrị ọnụ na-aga n'ebe ihe na-akpata bimetallic nwere ike ịka mma maka ngwaahịa ụfọdụ ezubere iche.Jaramillo na ndị ọrụ na-arụkọ ọrụ (96) rụpụtara sistemu bimetallic Au-Cu dị mfe, nke agbakwunyere site na ntinye ọla edo NP na polycrystalline Cu foil, iji nyochaa mmetụta catalysis tandem.Au-Cu bimetallic gosiputara nhọpụta mmekọrịta yana mmemme na mmanya C2+, na-egosipụta ọla kọpa na ọla edo dị ọcha, yana Au-Cu alloy.E jiri ya tụnyere Cu foil, usoro Au-Cu bimetallic gosipụtara mmụba CO nke mpaghara n'ihi ọnụnọ Au NP (Fig 6C) na-arụ ọrụ maka ọgbọ CO.Ebe ọla edo anaghị arụ ọrụ maka mbelata CO, agbakwunyere ọnụego mmepụta mmanya C2+ na Au-Cu bimetallic catalysts bụ usoro nke tandem catalysis.Kpọmkwem, NP ọla edo nwere ike iwepụta mkpokọta CO mpaghara dị nso na elu Cu.Na-esote, enwere ike ibelata mkpụrụ ndụ CO dị ukwuu na C2+ site na Cu.

(A ka C) Alloy mmetụta.(A) Kachasị FE nke ethanol na C2H4 na FE ratio nke ethanol na ethylene dị iche iche Cu-Zn alloys.(B) Njupụta ethanol dị ugbu a na ihe dị iche iche Cu-Zn.(A) na (B) ka ebigharịrị site na ikike sitere na American Chemical Society (38).(C) CO2 mbelata na CO evolushọn ọnụego na ọla edo, ọla kọpa, na Au-Cu bimetallic usoro.Mepụtaghachi ya site na ikike sitere na Nature Publishing Group (96).(D ruo L) Mkpesa ọmụmụ ma ọ bụ nhazi usoro.(D) Nleta atụmatụ nke usoro ịgba ígwè ion ígwè.(E na F) SEM onyogho nke 100-okirikiri Cu tupu (E) na mgbe (F) prereduction n'okpuru ECR ọnọdụ.(G) TEM na mpaghara eletrọn dị iche iche ahọpụtara tụrụ aro na ekpughere Cu (100) yana (H) ike efu maka * OCCO na * nhazi OCCHO na Cu (100), Cu (111), na akụkụ Cu (211).(D) ruo (G) ka emegharịrị site n'ikike sitere na Otu Nbipụta Nature (42).(I) Ratio nke oxygenates na hydrocarbons dị ka ọrụ nke nwere ike na Cu (111), Cu (751), na Cu (100).(J) Nọmba nhazi maka Cu (111), Cu (100), na Cu (751).(I) na (J) ka emegharịrị site na ikike sitere na National Academy of Sciences (97).(K) Atụmatụ nke usoro mgbanwe site na Cu NPs gaa na cubic-dị ka ọla kọpa.Emegharịrị site na ikike sitere na National Academy of Sciences (98).(L) onyonyo SEM nke ọla kọpa nanodendritic tupu na mgbe ECR gasịrị.Emegharịrị site na ikike sitere na American Chemical Society (99).

egosipụtawo nhọrọ nhọrọ nke ihu kristal maka ndị na-eme ka ọkụ eletrik dị ka ụzọ dị irè na nke ziri ezi iji nweta FE emelitere na ngwaahịa ECR kpọmkwem yana ụzọ dị mkpa maka nghọta bụ isi.Ngwakọta dị mfe mana nke nwere ike ịgbatị nke otu-crystal catalysts bụ ihe ịma aka.N'ịbụ onye sitere na usoro galvanostatic charging-discharging (GCD) maka batrị, otu anyị mepụtara usoro ịgba ígwè ígwè ion (Fig. 6D) iji họrọ kpughee akụkụ kristal nke Cu catalyst (42).Mgbe 100 GCD cycles, e guzobere nnukwu Cu nanocube array na Cu foil na ihu (100) ekpughere (Fig 6, E ruo G).Ihe na-eme ka 100-cycle catalyst gosipụtara mkpokọta mmanya C2 + FE karịa 30% yana njupụta mmanya mmanya C2 + kwekọrọ na nke karịa 20 mA cm-2.Otú ọ dị, 10-cycle Cu na ọnụ ala dị ala nke (100) facet nyere naanị C2 + mmanya FE nke ~ 10%.DFT simulation kwadoro na akụkụ Cu (100) na steepụ (211) dị mma maka C─C ijikọ n'elu Cu (111), dị ka egosiri na Fig. 6H.A na-eji ihe ngosi ihe atụ, ihe nkiri epitaxial Cu na akụkụ dị iche iche ekpughere, iji chọpụta ihe ndị na-arụ ọrụ na-arụ ọrụ na-eme ka C2 + oxygenate mmepụta (Fig. 6I) (97).Ebe ọ bụ na ọnụ ọgụgụ dị ntakịrị na CO * dimer dị n'akụkụ H * atom n'elu nke nwere ndị agbata obi ole na ole, saịtị Cu nwere ike igbochi nhazi nke hydrocarbons ma mee ka C2 + oxygenate FE dịkwuo mma n'ihi na ọ na-esiri ike hydrogenate. C─C jikọtara ECR etiti n'elu ya (97).N'ime ọmụmụ ihe nkiri epitaxial Cu, ndị edemede kwadoro na ECR na akụkụ Cu (751) gosipụtara oke oxygenate / hydrocarbon dị mma.Enwere ike ịkọwa nkwalite a n'elu Cu atom geometry nke akụkụ Cu dị iche iche na ọnụ ọgụgụ ahazi nke dị ala (Fig 6J), ebe Cu atom na-ahazi, n'otu n'otu, ya na ndị agbata obi abụọ, anọ na isii kacha nso na Cu(751). Cu (100), na Cu (111) ihu.Na ọnọdụ morphology nwughari ka ejirikwa kwalite C2+ oxygenate FE.Yang na ndị ọrụ na-arụkọ ọrụ (98) mepụtara cube nke na-arụ ọrụ, nke gosipụtara arụmọrụ C─C ka mma.N'ụzọ zuru ezu, monodisperse Cu NPs (6.7 nm) nwere dị iche iche loading ka etinyere na carbon akwụkwọ nkwado dị ka ihe na-akpali ECR.N'ụzọ doro anya, a hụrụ ụbara FE nke C2+ oxygenates na mmụba na ntinye Cu NP.E gosipụtara na Cu NP juru n'ọnụ n'okpuru ọnọdụ ibu dị elu mere mgbanwe mgbanwe ọnọdụ ọnọdụ n'oge ECR, bụ nke e mechara mepụta morphologies nke cube (Fig 6K).Achọpụtara ihe arụrụ arụ ọhụrụ a ka ọ na-arụ ọrụ ọkụ eletrik.Nyocha Tafel tụrụ aro na CO dimerization bụ usoro na-ekpebi ọnụego maka mmepụta ngwaahịa C2, ebe nke n-propanol gosipụtara ụzọ pụrụ iche na sistemụ catalytic a.Nanodendritic ọla kọpa bụ ihe atụ ọzọ na-egosi mkpa nke morphology akara maka C2 + oxygenate mmepụta (99).Na nkenke, ngụkọta FE nke ọla kọpa nanodendrite nke ọma (Fig 6L) maka mmanya C2 + bụ ihe dịka 25% na -1.0 V megide RHE.Enwere ike nweta nnukwu n-propanol FE nke 13% na -0.9 V. N'ịtụle ọrụ dị elu nke Cu atom, ndị na-eme ka ndị na-emepụta ọla kọpa na-ata ahụhụ mgbe niile site na mmebi nhazi n'oge ECR, karịsịa na nnukwu ike, nke, n'aka nke ya, na-eduga ná ndị dara ogbenye. nkwụsi ike.Otú ọ dị, ọla kọpa nanodendritic dị otú ahụ gosipụtara nkwụsi ike dị mma maka mmepụta mmanya na-aba n'anya, na-egosi mmanya FE nke ~ 24% karịa 6 awa.

Ọdịiche nke electrocatalysts, dị ka oghere atom na dopants, na-egosi ohere nke mgbasa ozi na-adịghị mma ECR intermediates na, si otú ahụ, na-ahọrọ na-eme ka ụzọ kwekọrọ ekwekọ na oxygenates (29, 43, 100).Na-ewere * C2H3O dị ka ihe atụ, nke bụ ike penultimate intermediate maka ethylene na ethanol mmepụta, Sargent na-arụkọ ọrụ (43) mụọ ọrụ nke ntụpọ na a core-shell Cu electrocatalyst n'ụzọ zuru ezu.Ha gosipụtara n'ụzọ doro anya na mmeghachi omume ike mgbochi maka ethylene na ethanol guzobe yiri na mmalite C─C njikọ njikọ (0.5-V overpotential) (Fig. 7A).N'okpuru ọnọdụ dị otú ahụ, iwebata ohere nke ọla kọpa ga-abawanye ntakịrị ihe mgbochi ike maka ịmepụta ethylene, ma ọ dịghị emetụta ọgbọ ethanol (Fig 7B).Otú ọ dị, dị ka e gosiri na fig. 7C, ọla kọpa catalysts na ohere ohere na subsurface sọlfọ dopant nwere ike ime ka ike dị ike maka ụzọ ethylene na-eme ka ọ ghara ịdị mma.Otú ọ dị, mgbanwe dị otú ahụ gosipụtara mmetụta na-adịghị mma na ụzọ ethanol.Ekwupụtakwara nnwapụta a ọzọ.Cu2S-Cu a haziri isi-shell nwere ohere dị ukwuu n'elu (Cu2S-Cu-V; Fig. 7D) ka arụpụtara.Ọnụ ọgụgụ nke mmanya na ethylene mụbara site na 0.18 na efu Cu NPs ruo 0.34 na Cu2S-Cu na-enweghị ohere na 1.21 na Cu2S-Cu-V, ọ bụ ezie na ngụkọta FE nke C2 + ngwaahịa maka ihe niile na-eme ka ọ dịgidere (Fig 7E) .Nlebanya a gosipụtara na nkwalite nke nhọrọ mmanya na-aba n'anya jikọtara ya na nkwụsị nke mmepụta ethylene, kwekọrọ na nsonaazụ DFT.Na mgbakwunye, injinia nwere nkwarụ na-arụ ọrụ dị mkpa karịa maka ikuku carbon na-enweghị igwe ebe ọ bụ na ihe carbon dị ọcha anaghị arụ ọrụ maka ECR.A na-eji dopants dị ka nitrogen na boron gbanwee usoro eletrọnịkị nke ihe na-akpata carbon (31, 43, 100).Dịka ọmụmaatụ, ihe nkiri nitrogen-doped nanodiamond (NDD) na mkpụrụ silik bụ Quan et al.(29) maka mmepụta acetate nhọrọ site na ECR (Fig 7F).Ike mmalite nke acetate dị ala dị ka -0.36 V na RHE site na iji NDD catalyst, na FE maka acetate karịrị 75% n'ogo nwere ike site na -0.8 ruo -1.0 V na RHE.Iji ghọta mmalite nke nkwalite dị egwu dị otú ahụ, a kwadebere ma nyochaa NDD / Si electrodes nwere ọdịnaya nitrogen dị iche iche ma ọ bụ ụdị nitrogen (Fig 7G).Ndị na-ede akwụkwọ kwubiri na arụmọrụ dị elu nke NDD/Si ​​catalyst maka ECR nwere ike ịsị na ọ dị elu maka evolushọn hydrogen na N doping, ebe ụdị N-sp3C na-arụsi ọrụ ike maka mmepụta acetate.Electrokinetic data na infrared spectrum situ gosiri na ụzọ bụ isi maka nhazi acetate nwere ike ịbụ CO2 → * CO2− → * (COO) 2 → CH3COO-.E wezụga nitrogen, boron bụ heteroatom ọzọ a nyochachara nke ọma iji chịkwaa usoro eletrọnịkị nke nanodiamond.Agbanyeghị, boron-doped nanodiamond (BDD) nke ọma belatara CO2 ka ọ bụrụ formaldehyde ma ọ bụ formate (101).Ọzọkwa, Quan na ndị na-arụkọ ọrụ (102) gosipụtara na boron na nitrogen co-doped nanodiamond (BND) gosipụtara mmetụta synergistic na ECR, nke nwere ike imeri njedebe nke BDD wee họrọ mmepụta ethanol.BND1, BND2, na BND3 ihe na-eme ka a kwadobere ọdịnaya nitrogen dị iche iche yana ọkwa doping boron yiri ya.Dị ka e gosiri na Fig. 7H, nhọrọ kachasị elu nke ethanol ruo 93% nwere ike nweta na BND3 catalyst na -1.0 V vesos RHE, nke nwere nitrogen doping kasị elu.Ngụkọta usoro ihe atụ gosipụtara na usoro njikọ C─C na BND dị mma nke ukwuu, ebe boron atom kwalitere ijide CO2 na nitrogen dopant mere ka hydrogenation nke etiti dị na ethanol.Ọ bụ ezie na heteroatom-doped nanodiamond nwere ike ịtụgharị CO2 ka ọ bụrụ multicarbon oxygenates na nhọrọ dị elu, ọrụ ECR ya dị oke oke n'ihi usoro nnyefe ngwa ngwa (njupụta ugbu a bụ ihe na-erughị 2 mA cm-2).Ihe dabere na graphene nwere ike ịbụ ihe ngwọta nwere ike imeri adịghị ike nke ihe na-eme ka diamond dabere.N'ụzọ doro anya, ewerela saịtị pyridinic N nke dị na oyi akwa graphene dị ka saịtị na-arụ ọrụ maka njikọ C─C (103).Nke a bụ n'ihi n'eziokwu na ọnụnọ nke pyridinic N na ebe nsọtụ nwere ike ime ka CO2 ghọọ CO, nke a ga-ejikọta ya na C2 + molecule (Fig 7I).Dịka ọmụmaatụ, etiti * C2O2 nwere ike kwụsie ike na carbon nitrogen-doped nke atọm C abụọ jikọtara na pyridinic N na atom C dị n'akụkụ ya, n'otu n'otu (103).Amụma amụma ahụ kwadoro site na iji nitrogen-doped graphene quantum dot (NGQD) catalysts (31).Mgbe a gbasasịrị akwụkwọ mpempe akwụkwọ graphene nitrogen-doped (1 ruo 3 μm) (Fig. 7J), 1- ruo 3-nm NGQD nwetara nke njupụta nke pyridinic N na ebe ihu na-abawanye site na iwu atọ dị ukwuu.Na -0.78 V na RHE, kacha FE maka C2 + oxygenates nwere ike iru ruo 26%.Tụkwasị na nke ahụ, dị ka e gosiri na Fig. 7K, njupụta nke ugbu a maka C2 + oxygenates dị nso na 40 mA cm-2 na -0.86 V na RHE, nke dị elu karịa nke nanodiamond gbanwere.N'iji ya tụnyere, N-free graphene quantum dots na N-doped graphene oxide, nke na-egosi ebe pyridinic N dị ala dị ala, na-ebute H2, CO, na formate.

(A ruo C) Gibbs ike efu sitere na * C2H3O ruo ethylene na ethanol maka ọla kọpa, ọla kọpa nwere ohere, yana ọla kọpa nwere oghere ọla kọpa na sọlfọ dị n'okpuru.(D) Nleta atụmatụ nke ihe nrụpụta Cu2S-Cu-V.(E) FE nke C2 + alcohols na ethylene, yana oke FE nke alcohols na alkenes.A na-ebipụtaghachi (A) ruo (E) site n'ikike sitere na Òtù Na-ebipụta Nature (43).(F) Foto SEM nke NDD.(G) Ọnụego mmepụta nke acetate na formate na NDD nwere ọdịnaya nitrogen dị iche iche.na %, atomic %.(F) na (G) ka emegharịrị site na ikike sitere na American Chemical Society (29).(H) FEs maka NDD, BDD, na BND na -1.0 V. Megharịrị site na ikike sitere n'aka John Wiley na Ụmụ (102).(I) Ntụle atụmatụ nke saịtị ndị na-arụ ọrụ maka njikọ C─C na NGQDs.(I) ka emegharịrị site na ikike sitere na American Chemical Society (103).(J) onyonyo TEM nke NGQD.Ogwe ọnụ ọgụgụ, 1 nm.(K) Njupụta dị ugbu a maka ngwaahịa dị iche iche na-eji NGQD.(J) na (K) ka ewegharịrị site na ikike sitere na Otu Nbipụta Nature (31).

Na-abụghị electrocatalysts, electrode na catalytic reactor architecture imewe na-eweta ụzọ ọzọ dị irè iji kwalite arụmọrụ ECR, ọkachasị maka ọnụego mmepụta na arụmọrụ ike.Emeela ọganihu dị ịrịba ama na imewe na imepụta usoro electroreduction ọhụrụ iji nweta mmepụta C2+ nke ọma.Na ngalaba a, anyị ga-atụle ECR electrode/reactor imewe n'ụzọ zuru ezu.

A na-eji mkpụrụ ndụ ụdị H eme ihe nke ukwuu n'ule nyocha ụlọ nyocha, na-atụle mgbakọ ngwa ngwa ha, ọrụ dị mfe na ọnụ ala.A na-eji sel ndị ahụ nwere cathode nọọrọ onwe ha na ọnụ ụlọ anode nke jikọtara ya na akpụkpọ anụ mgbanwe ion (104, 105).Ihe kachasị njọ nke ụdị H-ụdị cell a bụ obere CO2 solubility na electrolyte aqueous, nke bụ nanị 0.034 M n'okpuru ọnọdụ ọnọdụ, na-eduga na njedebe CO2 mbelata njupụta ugbu a nke j <100 mA cm-2 (64).Ọzọkwa, ihe ndọghachi azụ ndị ọzọ dị n'ime, gụnyere oke ikuku elektrọd na nnukwu anya interelectrode, emezubeghị ihe nyocha na-eto eto (105, 106).Maka ọgbọ ngwaahịa C2 +, mkpụrụ ndụ ụdị H na-egosipụtakarị nhọrọ dị ala n'okpuru ike dị elu, dịka, 32% maka ethylene na -0.98 V na RHE (107), 13.1% maka n-propanol na -0.9 V vs RHE (99), na 20.4% maka ethanol na -0.46 V megide RHE (108), n'ihi mgbanwe mgbanwe hydrogen siri ike.

Iji dozie okwu ndị dị n'elu, a tụrụ aro reactor eruba (15, 109).N'ime mkpụrụ ndụ na-asọpụta, enwere ike iji iyi CO2 gaseous dị ka nri nri na cathode, si otú a na-eduga n'ịbawanye mgbasawanye na oke mmepụta (104, 110).Onyonyo 8A na-egosi ụdị ihe owuwu nke cell eruba, ebe polymer electrolyte membrane (PEM) jere ozi dị ka ihe nkesa electrode nke a na-agbanye n'etiti ọwa abụọ eruba.A na-emegharị ihe na-eme ka ọ banye na ikuku mgbasa ozi gas (GDE) ka ọ rụọ ọrụ dị ka electrode cathode, nke a na-enye gas CO2 nri ozugbo.The catholyte, dị ka 0.5 M KHCO3, na-aga n'ihu na-asọpụta n'ime mkpa oyi akwa n'etiti catalyst electrode na PEM.Tụkwasị na nke ahụ, a na-ekesa akụkụ anode na electrolyte aqueous maka mmeghachi omume evolushọn oxygen (43, 110).E jiri ya tụnyere mkpụrụ ndụ ụdị H, mkpụrụ ndụ na-asọpụta na akpụkpọ ahụ ndị a na-egosi arụmọrụ ECR dị elu nke ukwuu.Dịka ọmụmaatụ, Sargent na ndị ọrụ (43) nyochaa arụmọrụ ECR nke Cu2S-Cu-V catalyst na ma ụdị H-ụdị cell na cell flow cell, dị ka e gosiri na 8 (B ruo E).N'iji mkpụrụ ndụ ụdị H, kacha FE maka ngwaahịa C2 + bụ 41% na njupụta ugbu a nke ~ 30 mA cm-2 n'okpuru -0.95 V na RHE.Otú ọ dị, FE maka ngwaahịa C2 + mụbara ruo 53% na njupụta ugbu a dị mfe karịa 400 mA cm-2 n'okpuru -0.92 V vesos RHE na usoro ntinye.Ọganihu arụmọrụ dị otú ahụ site na iji reactor na-eru eru nwere ike ịsị na ọ bụ mgbasawanye CO2 na mmeghachi omume n'akụkụ, na-esite na ụlọ gas-electrolyte-catalyst nke ime obodo.

(A) Eserese nke electrolyzer na-asọpụta nwere atụmatụ mbugharị nke ihe nrụnye electrode-electrolyte.A na-ebipụtaghachi (A) site na ikike John Wiley na Sons (30).(B ruo E) Tụnyere arụmọrụ ECR site na iji cell ụdị H na cell eruba.(B) ruo (E) ka emegharịrị site n'ikike sitere na Otu Nbipụta Nature (43).(F ruo H) electrolytes dị iche iche etinyere na sel na-asọpụta na arụmọrụ ECR.(F) ruo (H) ka emegharịrị site na ikike sitere n'aka John Wiley na Ụmụ (30).(I ruo K) Nrụ ọrụ na nkwụsi ike nke electrode mgbasa gas nke dabere na polymer.(I) ruo (K) ka emegharịrị site na ikike sitere na AAAS (33).

Mkpụrụ ndụ oghere efu bụ klaasị ọzọ na-apụta nke electrolyzers, nke na-ewepụkwa ọwa eruba na sel na-asọpụta wee pịa electrodes abụọ yana akpụkpọ ahụ mgbanwe ion n'etiti.Nhazi a nwere ike ibelata mbufe oke na nguzogide nfefe eletrọn wee si otú a kwalite arụmọrụ ike, na-eme ka ọ dịkwuo mfe na ngwa bara uru (110).Ndị na-emeghachi omume na-eri nri na cathode nwere ike ịbụ ma ọ bụ CO2-saturated catholyte ma ọ bụ ikuku CO2 iru mmiri.A na-enyefe mmiri vapor ma ọ bụ aqueous electrolyte na anode maka ntọhapụ proton iji kwụọ ụgwọ maka ụdị mbelata CO2 (111).Gutiérrez-Guerra et al.(109) nyochara arụmọrụ nke ngwakọ ngwakọ Cu-AC na cell gap efu wee kọọ na acetaldehyde bụ isi ngwaahịa nwere oke nhọrọ nke 60%.Dị ka ihe ọzọ uru nke ngwaọrụ a, ọ dị nnọọ mfe pressurize reactant eruba na budata welie mpaghara CO2 ịta, si otú a na-akpata nnukwu ugbu densities na elu mmeghachi omume ọnụego (110).Otú ọ dị, ọnụ ọgụgụ mgbanwe ion accelerated na sel oghere efu na-achọ acidify na catholyte, na-agbanwe mmeghachi omume na H2 evolushọn kama CO2 Mbelata (112).Iji dozie nsogbu a, Zhou na ndị ọrụ ibe (112, 113) na-etinye oyi akwa mkpuchi na electrolyte na-ekesa n'etiti cathode na akpụkpọ ahụ iji nọgide na-enwe pH kwesịrị ekwesị n'akụkụ cathode maka mmeghachi omume mbelata CO2.Ọ bụ ezie na achọpụtara ngwaahịa C2 + dị iche iche na ndabere nke mkpụrụ ndụ oghere efu, gụnyere acetone, ethanol, na n-propanol, FE ka dị ntakịrị.Ọtụtụ ọmụmụ a na-akọ na-elekwasị anya na ngwaahịa C1 na-agụnye ọnụọgụ proton na eletrọn ole na ole n'oge mmeghachi omume mbelata.Ya mere, ohere nke oghere efu efu maka ngwaahịa C2 + ka na-arụrịta ụka (110).

Ọzọkwa, sel microfluidic electrolytic (MECs) bụ ụdị nhazi electrolyzer na-adọrọ mmasị nke ukwuu nke Kenis na ndị ọrụ na-arụkọ ọrụ mepụtara (39, 114).Na ngwaọrụ a, akpụkpọ ahụ na-anọchi anya oghere dị mkpa (<1 mm na ọkpụrụkpụ) jupụtara na mmiri electrolyte na-asọ asọ iji kewaa anode na cathode.Ụmụ irighiri ihe CO2 nwere ike gbasaa ngwa ngwa n'ime interface electrode-electrolyte dị nso na cathode, na GDE abụọ a kapịrị ọnụ na-agbanye site na electrolyte na-asọ asọ.E jiri ya tụnyere mkpụrụ ndụ na-eruba n'ime akpụkpọ ahụ, MEC ọ bụghị naanị na-ezere ọnụ ahịa akpụkpọ ahụ dị elu kamakwa na-ebelata njikwa mmiri, nke na-ezo aka na idei mmiri anode na-apụ apụ na cathode mgbe ejiri ya na njupụta dị elu ugbu a n'ihi mmịpụta osmotic nke mkpụrụ ndụ mmiri yana. mbufe proton site na anode gaa cathode gafee akpụkpọ ahụ (115).Dị ka anyị maara, n'agbanyeghị uru na mmezu ndị a na-ahụ anya, ọnụ ọgụgụ dị nta nke ọmụmụ enwetala ngwaahịa C2+ na MEC mbụ.Nke a nwere ike ịbụ mmetụta "na-ese n'elu mmiri" nke na-esi na mpaghara cathode dị nso ma ọ bụ na-asachapụ ya na protons na-emepụta na anode, kama itinye aka na ọtụtụ proton chọrọ C2+ mmeghachi omume nhazi.Enwere ike ịkwado ntule ahụ site na ihe atụ na-esonụ.Na 2016, Kenis na ndị ọrụ (31) kọrọ na mbelata nke ọma nke CO2 na ngwaahịa C2 + na mgbanwe mgbanwe na akpụkpọ ahụ nwere MEC, nke NGQD nwere ike belata CO2 molekul na C2 + na 55% FE (31% maka ethylene, 14% maka ethanol, 6% maka acetate, na 4% maka n-propanol) na ikike etinyere nke -0.75 V na RHE na 1 M KOH ngwọta.Ọ dị mkpa ịkọwapụta na gburugburu electrolyte nwere ike imetụta nhọrọ nhọrọ ngwaahịa.Dịka ọmụmaatụ, Jiao na ndị ọrụ na-arụkọ ọrụ (30) na-emepụta nanoporous Cu catalyst wee nwalee arụmọrụ ECR ya site na iji electrolytes dị iche iche (KHCO3, KOH, K2SO4, na KCl) na MEC dabeere na akpụkpọ ahụ.Ha kpughere na CO2 mbelata na alkaline electrolyte (KOH) na-egosipụta C2 + selectivity kasị elu na njupụta ugbu a, dị ka e gosiri na 8 (F na G).Na -0.67 V na RHE na 1 M KOH electrolyte, enwetara FE maka C2 + ruru 62% na njupụta dị ugbu a nke 653 mA cm-2, nke bụ otu n'ime njupụta kachasị elu ugbu a nke akọtụrụla na mbelata electrochemical CO2. maka ngwaahịa C2+.Ethylene (38.6%), ethanol (16.6%), na n-propanol (4.5%) bụ isi ngwaahịa C2 + na obere ego nke acetate.Ha gosikwara na enwere njikọ siri ike n'etiti pH gbakọọ na FE maka ngwaahịa C2 +: Nke dị elu nke elu pH, njupụta dị ugbu a na ngwaahịa C2 + na-emepụta, dị ka e gosipụtara na Fig. 8H.Ngụkọ usoro ihe atụ tụrụ aro na OH-ion dị nso nwere ike ịkwado njikọ C─C siri ike (31).

Na mgbakwunye na nhazi nke electrolyzer, electrolyte etinyere na electrolyzers dị iche iche nwekwara ike gbanwee ngwaahịa ECR ikpeazụ.Dị ka anyị kwuru n'elu, nnukwu alkaline KOH ngwọta na-mgbe niile na-eji na eruba sel na-arụ ọrụ magburu onwe ya kama na H-ụdị sel.A na-ekwu na eziokwu ahụ bụ na KOH electrolyte nwere ike inye conductivity electrolyte dị elu, belata nguzogide ohmic n'etiti mkpuchi electrolyte dị mkpa na catalyst na nnukwu electrolyte, ma na-ebelata ihe ndị achọrọ maka ịmepụta C2+ (31).Nsonaazụ DFT na-akwadokwa na ọnụnọ nke OH-ion nwere ike belata ihe mgbochi ike maka dimerization CO, si otú a na-akwalite nhazi C2 + ma na-egbochi asọmpi site na nhazi C1 na H2 (30, 33).Agbanyeghị, enweghị ike iji alkaline KOH dị ka electrolyte na sel ụdị H.Nke a bụ n'ihi na iyi CO2 ga-eme ngwa ngwa na ngwọta KOH ma mesịa mepụta ngwọta bicarbonate na pH na-anọpụ iche na sel H-ụdị (30).N'ime sel ndị na-asọpụta, Otú ọ dị, ozugbo CO2 na-agbasa site na GDE, a ga-eri mkpụrụ ndụ CO2 na njedebe nke okpukpu atọ (CO2-catalyst-electrolyte) iji mepụta ngwaahịa belata ozugbo.E wezụga nke ahụ, adịghị ike buffering ikike nke electrolyte na-enwe ike ngwa ngwa mụbaa pH gburugburu electrode na guzo electrolyzer nhazi, ebe ndị na-erugharị electrolyte ga-eme ka elu ma belata pH fluctuation na electrolyte (33, 116).

Dịka e kwuru na mbụ na ECR bụ mmeghachi omume na-achịkwa mgbasa, nrụgide mmeghachi omume dị elu nwekwara ike ime ka ọnụọgụ CO2 dịkwuo ukwuu na interface.Ndị na-emegharị nrụgide dị elu na-adịkarị ka igwe anaghị agba nchara autoclave, nke nwere ike ịme ka CO2 nrụgide dị elu (ruo 60 ATM) n'ime cell, na-eduga na mmụba dị ịrịba ama na ma FE na njupụta dị ugbu a nke C2 + (117). , 118).Sakata na ndị ọrụ na-arụkọ ọrụ (119) gosiri na enwere ike imeziwanye njupụta dị ugbu a na 163 mA cm-2 n'okpuru 30 atm na Cu electrode na ethylene dị ka isi ngwaahịa.Ọtụtụ ihe na-eme ka ígwè (dịka, Fe, Co, na Ni), na-enweghị ọrụ maka mmepụta C2 + na nrụgide ambient, nwere ike ibelata CO2 na ethylene, ethane, propane, na ngwaahịa C2 + ndị ọzọ dị elu na nrụgide dị elu.Egosiputara na nhọpụta nke ngwaahịa ndị a na-adabere na nrụgide CO2 n'ụzọ nke ịgbanwe ọdịdị CO2 na elu electrode (117, 120).A na-agbanwe ngwaahịa ndị isi belatara site na H2 gaa na hydrocarbons (C2+ gụnyere) na nke ikpeazụ na CO/HCOOH nwere nrụgide CO2 mụbara.N'ụzọ doro anya, ekwesịrị iji nlezianya nyochaa nrụgide CO2 n'ihi na nrụgide CO2 dị elu ma ọ bụ dị ala ga-eme ka ọnụọgụ CO2 dị oke ma ọ bụ njedebe, nke na-akwado mmepụta nke CO/HCOOH ma ọ bụ H2.Naanị ọnụọgụ CO nke etiti na njupụta dị ugbu a nke na-emepụta n'elu electrode nwere ike ịkwado mmeghachi omume C─C ma kwalite C2+ ngwaahịa selectivity (119).

Ịmepụta electrode akwụkwọ akụkọ nwere ihe owuwu dị elu bụ ntụzịaka ọzọ dị mkpa iji kwalite mmepụta C2+ ahọpụtara.N'oge mmalite, electrodes na-arụ ọrụ bụ ihe mkpuchi igwe na-adịghị mma ma na-ata ahụhụ site na nnyefe uka dị umengwụ (26, 105).N'ihi ya, a tụrụ aro GDE iji belata arụ ọrụ cell na-adịghị mma site n'inye ọwa hydrophobic nke na-eme ka mgbasawanye CO2 na-eme ka ihe na-eme ka ahụ dịkwuo mma (121).GDE nke a na-emekarị na-enwekarị oyi akwa ihe na-akpata (CL) na oyi akwa mgbasa gas (GDL), dịka egosiri na akụkụ ala nke Fig. 8A (30, 33).Igwe gas-liquid-catalyst interface emebere na GDE dị oke mkpa iji melite arụmọrụ cell.GDL jikọtara ya na ihe ndị nwere porous (nke bụ akwụkwọ carbon) nwere ike inye ọtụtụ ụzọ CO2 ma hụ na ọnụego mgbasa electrolyte ngwa ngwa.Ọ na-arụkwa ọrụ dị ka ụzọ ụgbọ njem dị ala maka protons, elektrọn, na ngwaahịa mbelata sitere na CL n'ime electrolyte (121).Ntube nkedo, ikuku ikuku, na electrodeposition bụ teknụzụ a na-ahụkarị maka nkwadebe nke GDEs (122).Achọpụtala ihe na-eme ka ndị na-emepụta ihe gbakọtara na GDEs na CO2 electroreduction na ngwaahịa C2+.N'ụzọ doro anya, sel ndị na-erugharị ahụ e kwuru n'elu nwere arụmọrụ dị mma jikọtara ya na GDE.N'ihe dị ka 1990, Sammells na ndị ọrụ (123) kọrọ na Cu-coated GDEs nwetara FE dị elu nke 53% maka ethylene nwere nnukwu njupụta nke 667 mA cm-2.Ịkwalite nhọrọ nke ethylene na ethanol bụ nnukwu ihe ịma aka nke a na-emepụta mgbe niile na ihe ndị na-akpata Cu n'ihi ụzọ mmeghachi omume ha yiri nke ahụ.Ọzọkwa, ọ dị mkpa ịkọwapụta na arụpụtaghị ihe dị elu na nhọrọ nke ethylene ma e jiri ya tụnyere ethanol ka achọpụtara na Cu-based GDE (25, 36).Gewirth na ndị ọrụ na-arụkọ ọrụ (36) gosipụtara ezigbo FE nke 60% maka ethylene na FE nke emechiri emechi maka ethanol nke 25% na Cu-Ag GDE electrodeposited, mgbe ngụkọta nke ugbu a ruru ~ 300 mA cm-2 na -0.7 V vesos. RHE.Ọ bụ ọrụ na-adịghị ahụkebe nke nwetara oke nhọrọ dị otú ahụ na njupụta dị ugbu a.Nchoputa a na-egosi na GDE-webatara electrode na-enye ụzọ dị mma maka ịhazigharị ụzọ mmeghachi omume, nke enwere ike ịnweta nhọrọ nke ngwaahịa ndị na-ebelata na njupụta dị ugbu a.

Nkwụsi ike nke GDEs bụkwa okwu dị mkpa kwesịrị ileba anya n'ihi na ịrụ ọrụ ogologo oge kwụsiri ike dị mkpa iji nweta ngwa bara uru maka mkpụrụ ndụ na-asọpụta.N'agbanyeghị arụmọrụ CO2-to-C2+ pụtara ìhè enwetara na GDEs, nkwụsi ike ahụ ka na-adịghị mma n'ihi nrapagide arụrụ arụ na-adịghị ike nke ihe nrụnye, GDL, na akwa akwa (77, 124).Elu carbon nke GDL nwere ike gbanwee site na hydrophobic gaa na hydrophilic n'oge mmeghachi omume electrochemical n'ihi mmeghachi omume oxidation nke mere na ike dị elu, nke na-eduga na idei mmiri na GDL na mgbochi CO2 mgbasa ụzọ (33).Iji dozie nsogbu a, ndị nchọpụta jikọtara hydrophobic scaffold nke polytetrafluoroethylene (PTFE) n'ime GDEs.E jiri ya tụnyere hydrophilic Nafion, oyi akwa PTFE hydrophobic na-enye nkwụsi ike ogologo oge dị elu (33).Sargent na ndị ọrụ (33) kpọkọtara Cu catalyst n'etiti PTFE kewapụrụ na carbon NP, nke hydrophobic PTFE oyi akwa nwere ike immobilize NPs na graphite n'ígwé, si otú na-ewu a kwụsiri ike electrode interface (Fig. 8, I na J).N'ihi ya, FE maka mmepụta ethylene mụbara na 70% na ngwọta 7 M KOH na njupụta dị ugbu a nke 75 ruo 100 mA cm-2.Ogologo ndụ nke reactor eruba a gbatịpụrụ ihe karịrị awa 150 na enweghị mfu na ethylene selectivity, nke dị okpukpu 300 karịa GDE omenala, dị ka egosiri na Fig. 8K.Egosiputala usoro Sanwichi dị otú ahụ ka ọ bụrụ ezigbo atụmatụ GDE.Dịka ọmụmaatụ, Cui na ndị ọrụ na-arụkọ ọrụ (124) haziri ihe owuwu trilayer nwere oyi akwa electrode na-arụ ọrụ nke ihe nkiri polyethylene abụọ hydrophobic nanoporous chịbiri.N'ígwé nke hydrophobic nke dị n'èzí nwere ike ime ka ikuku electrolyte kwụsị site na ngwọta dị ukwuu, na-eduga n'ịdị elu, pH dị elu na mpaghara gburugburu electrode na-arụ ọrụ.Nkwalite nke oghere interlayer, nke nwere ike melite njem CO2 na mgbasa ozi, dịkwa mkpa na nhazi dị otú ahụ (124).N'oge na-adịbeghị anya, carbon nanotubes abanyekwala n'ime GDEs n'ihi oke porosity ha, ezigbo conductivity, na hydrophobicity, nke nwere ike ịkwado electron na njem njem (77).

N'agbanyeghị ọganihu na-akpali akpali na ECR, atụmatụ maka ọnụ ala dị ala, nnukwu ọnụ ahịa ngwaahịa C2 + adịghị adịkarị (125).N'oge a, ihe ịma aka na ohere dị n'otu oge ịghọta usoro mmeghachi omume nke ECR na ịzụ ahịa teknụzụ a na-ekwe nkwa.

Dị ka ihe ngwọta mara mma iji mechie loop carbon ma chekwaa ume ọhụrụ na-agbanwe agbanwe, dị ka ikuku na anyanwụ, enweela ọganihu dị ukwuu iji nweta ntụgharị CO2 nke ọma n'ime iri afọ gara aga.Ọ bụ ezie na nghọta nke usoro metụtara ECR abịawo ogologo oge kemgbe mmalite ya (126), njikọ C─C site na ECR na ngwaahịa C2 + ka dị anya maka ngwa bara uru.Na nyocha a, anyị lere anya nke ọma na atụmatụ ndị dị ugbu a nke nwere ike ịkwalite nhọrọ na mmepụta ihe maka ngwaahịa C2 + site na ECR, gụnyere nhazi nke ọma, mmetụta electrolyte, ọnọdụ electrochemical, na electrochemical electrode/reactor design.

N'agbanyeghị mgbalị niile a na-etinye na ECR, a ka nwere ọtụtụ nsogbu na ihe ndị na-eme ka ọ dị ugbu a na usoro ECR nke a ga-edozi tupu ịzụ ahịa ECR.Mbụ, dị ka ndị na-achị akpali akpali ịghọta ịrụ ọrụ nke ọma C ─C njikọ, Cu na-ata ahụhụ si oké nkwụsi ike okwu, karịsịa na aqueous electrolyte, na ike adịkarịghị adị ndụ ruo 100 awa n'ihi na ha elu atom ngagharị, urughuru mkpokọta, na Ọdịdị emebi n'okpuru ECR ọnọdụ.Ya mere, otu esi enweta nkwụsi ike ogologo oge site na iji ihe nke dabeere na Cu ka bụ ihe ịma aka mepere emepe.Idokwa ihe mkpata dabere na Cu na nkwado a kapịrị ọnụ yana mmekọrịta siri ike nwere ike ịbụ atụmatụ a pụrụ ịdabere na ya iji chekwaa usoro ihe na-akpali akpali ma si otú a na-enye ogologo ndụ.Ọzọkwa, iji polymer membrane electrolyte dochie ihe ngwọta mmiri n'oge ECR nwere ike ime ka nkwụsi ike nke Cu-based catalyst.Tụkwasị na nke ahụ, site n'echiche nke ndị na-emepụta ihe, na situ / na operando ekwesịrị iji usoro njirimara njirimara na nhazi usoro ihe atụ iji nyochaa ma ghọta mmebi arụmọrụ nke na-akpata, ya mere, n'aka nke ya, na-egbochi mmebi na nsị nke ihe na-eme ka ọ bụrụ ọkwa kachasị elu.Ihe ọzọ dị mkpa nke ihe ndị na-eme ka ECR kwesịrị ilebara anya bụ ime ka usoro njikọ ahụ nwee ike ime ka mmepụta ihe dị ukwuu.Iji mezuo nke a, a na-ahọrọ ịhazi usoro sịntetik site na iji nri nri dị ebe niile.

Nke abụọ, a na-agwakọta C2 + oxygen sitere na ECR na solutes (dịka ọmụmaatụ, KHCO3 na KOH) na electrolyte maka ndị na-emegharị H- ma ọ bụ na-eruba-cell, nke, Otú ọ dị, chọrọ mmezi nkewa na nhazi usoro iji nwetaghachi ngwọta mmanụ ọkụ dị ọcha. ngwa bara uru.N'otu oge ahụ, a na-agwakọta C2+ hydrocarbons na H2 na CO2 fọdụrụnụ.Ya mere, usoro nkewa dị oke ọnụ dị mkpa maka teknụzụ ECR dị ugbu a, nke na-egbochi ECR site na ngwa bara uru.Ya mere, otu esi emepụta ihe ngwọta mmanụ ọkụ dị ọcha na gas dị ọcha, karịsịa na nnukwu ngwaahịa ngwaahịa, bụ ihe na-achọsi ike maka ntinye ECR dị irè.Anyị si otú ahụ buru amụma ịrị elu nke ọgbọ nke ngwaahịa dị ọcha site na ECR n'ọdịnihu dị nso, nke nwere ike iburu teknụzụ ECR nso na ahịa (127).

Nke atọ, ebe nguzobe nke C─O na C─H, dị ka ethanol, acetic acid, na ethylene, na nkà na ụzụ ECR ka a na-amụ nke ọma, nchọpụta ụdị ngwaahịa ndị ọzọ dịkwa mkpa maka nkà na ụzụ ECR ma gosipụta mmasị akụ na ụba.Dịka ọmụmaatụ, n'oge na-adịbeghị anya, Han na ndị ọrụ ibe (128) kọrọ mmepụta nke 2-bromoethnol site na ECR.Nhazi ọnọdụ nke C─Br bond na-agbanwe ngwaahịa ahụ site na ethanol gaa na 2-bromoethnol, nke bụ ihe dị mkpa na-ewu ụlọ na kemịkalụ na ọgwụ na-egosi uru agbakwunyere dị elu.Ya mere, gafere ngwaahịa C2 + nke a na-amụ nke ọma ugbu a, anyị kwenyere na ịchụ ntanye ngwaahịa ndị ọzọ a na-adịghị ahụkebe dị ka oxalic acid (129) na njikọ nke mkpụrụ ndụ C2+ dị mgbagwoju anya dị ka ogige cyclic bụ ụzọ ọzọ na-ekwe nkwa maka nyocha ECR n'ọdịnihu.

N'ikpeazụ ma ọ dịghị ihe ọzọ, akwụkwọ akụkọ electrode na reactor chepụta dị ka waterproof GDE, mmiri mmiri na-erugharị sel, na PEM cell kwesịrị ka a nakweere n'ọtụtụ ebe iji kwalite ọnụego mmepụta ECR na ọkwa azụmahịa (> 200 mA cm-2).Otú ọ dị, a na-ahụ nnukwu ọdịiche dị na ọrụ electrocatalytic mgbe a na-etinye electrocatalysts na ule cell zuru ezu.Ya mere, a ga-emekwu ọmụmụ ihe n'usoro iji belata ọdịiche dị n'etiti ọmụmụ ihe ọkara cell na ngwa ngwaọrụ zuru ezu iji weta ECR site na ule nyocha ụlọ nyocha iji mee ihe bara uru.

Na nchịkọta, mbelata electrochemical CO2 na-enye anyị ohere dị mma iji dozie nsogbu gburugburu ebe obibi sitere na gas griin haus na-ebute site na ọrụ mmadụ.Ọ na-egosikwa ohere ị nweta mmanụ ọkụ na kemịkalụ dị ọcha site na iji ume ọhụrụ.Ọ bụ ezie na ọtụtụ ihe ịma aka na-anọgide maka nkà na ụzụ ECR na ọkwa dị ugbu a, karịsịa maka usoro njikọ C─C, a kwenyere na site n'ịga n'ihu na nyocha na mmepe na njikarịcha catalyst na izu okè cell, echiche nke ezigbo CO2 electrolysis maka mmanụ dị ọcha. na kemịkalụ ga-emezu n'ọdịnihu dị nso.

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