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Catalysts 2020, 10, x FOR PEER REVIEW 12 of 25 polycrystalline Cu electrodes upon reduction, tuning the selectivity of ethanol formation [67]. A Catalysts 2020, 10, 1287 12 of 25 maximum ethanol FE of 31% was achieved on a polycrystalline Cu electrode with an N-tolylpyridinium chloride additive in a CO2-saturated 0.1 M KHCO3 electrolyte at −1.1 V vs. RHE. Belescitdreosdtehuiss,inagnaNn,oNs’t-reutchtyulrende-Cpuhenleacntrthordoeliunsiuinmg Ndi,bNr’o-methidyeleanse-apmheonlaencuthlarorlaindiduimtivdeibisrocmapidabelaesoaf mfoormlecinuglaertahdadniotlivweiitshcapFaEbolef o15f%fordmuirninggetChOanorlewduitchtioanFEato−f1.50%7 Vduvrsi.nRgHCEO2inre0d.1ucMtioKnHaCt −O1.0[768V]. 23 vTsh.eRoHrgEaninic0m.1oMlecuKlHeCsuOc3h[6a8s]1.-Tohcteadoergcaneicthmioollceacnulaelsoucbheuase1d-otoctamdoedcaifnyetheiodlecnatnritailcsoCubeluecsetrdodtoe wmiotdhihfydthroepdheonbtircitiyc [C69u]. eBleycstruordpereswsitnhg hHyEdRro, pthiosbkiicnitdyo[f6h9y].dBroyposubricpreelesscitnrogdeHaEtRta,inthsi1s7k%inFdE of −2 -2 hetyhdarnooploabtic−e3l0ecmtrAod·cemattains01.17%MFCEsoHfCetOhancolmapta−r3e0dmtoA·4c%monina0.h1yMdroCpshHiClicOe3qcuomivpalaernetd. tAon4o%thoenr 3 aexchiytidnrgoepxhaimlicpleqiusitvhaelepnotr.pAhynrointh-berasedxcmitientgalliecxcaompplelexis(5t,h10e,1p5o,2r0p-hteytrianp-hbeanseydl-2m1Het,2a3llHic-pcormphpilnexe (ir5o,1n0(,I1I5I),2c0h-ltoetrridapeh, FeneTylP-2P1[CHl,]2)3fHun-pcotiropnhailnizeinirgonC(IuIIs)ucrhflaocrei,dwe,hFiecThPcPa[nCpl]r)ofvuindcetionntearlimziendgiaCteu-CsuOr-fraiceh, wlohcaiclhencvainropnrmoveindtethinateframcielditiaattees-CO-C-rciochuplolicnagl aenvdirsotenemrsetnhtetrheaatcftaiocniliptattehswCa-yCtocowuaprldinsgetahnadnoslte[7e0rs]. tBhye inretearcgtiroantinpgatiht winatyo atoflwoawrdscelelthsyanstoelm[,70th].e BFyeTiPnPte[Crgl]r-aftuingctioitnainlitzoedaCfulowelecterloldseyestxehmib,ittshea −2 FCeOTP-tPo[-Cetl]h-afunnolctFiEonoafl4iz1e%d aCnud aelpeacrtrtioadl ecuerxrhenibtidtsenasiCtyOo2f-t−o-1e2t4hmanAo·lcmFE oaft4−10%.82anVdvsa. pRaHrtEia(lFicgurren5)t. density of −124 mA·cm−2 at −0.82 V vs. RHE (Figure 5). Figure 5. (A(A)) SSccheemaatticic iilllussttrraattioionn off CO2--ttoo--eetthhaannooll paatthwaayy ffavorred by locally generated 2 high-concentratiionCOoonnFFeeTTPPP[C[Cl]l]fufnucntciotinoanlaizliznigngCuCususrufarcfaec,ea,nadnCdOC2-Oto-etoth-eytlhenyelenpeathpwatahywoany 2 boanrebaCrue Csurfsaucref.a(cBe). E(Bth)aEntohlaFnEolaFnEd a(Cnd) p(aCr)tipalarctuiarlrecnutrrdeentsidtyennsoitrymnaolirzmedalibzyedgeboymgeetroimc aertreiac oavrear FoevTerPPFe[CTlP]/PC[Cul]a/nCdu aCnudcCautaclyastatslyastsvaatrvioaurisouapspapliepdliepdopteontetinatlisa.lsR.eRperpodroudcuedcedwwithithpperemrmisisisoinon[7[700]].. 2 Copyright 2020, Macmillan Publishers. Copyright 2020, Macmillan Publishers. 3.1.2. Cu Alloy 3.1.2. Cu Alloy Coupling another metal with Cu, as a form of interface engieering has been suggested as an Coupling another metal with Cu, as a form of interface engieering has been suggested as an effective strategy to break the conventional scaling relationships and tune the binding energy of effective strategy to break the conventional scaling relationships and tune the binding energy of targered intermediates on Cu surface, thus enhancing the reaction kinetics and selectivity for CO2 targered intermediates on Cu surface, thus enhancing the reaction kinetics and selectivity for CO2 reduction [89,90]. It is promising to design Cu bimetallic electrocatalysts, which will possess intriguing reduction [89,90]. It is promising to design Cu bimetallic electrocatalysts, which will possess catalytic behavior with respect to that of single-metal electrocatalysts. Those metals (such as Au, intriguing catalytic behavior with respect to that of single-metal electrocatalysts. Those metals (such Ag, Zn and Pd) with CO as the main product could provide abundant CO to couple with the key as Au, Ag, Zn and Pd) with CO as the main product could provide abundant CO to couple with the intermediate *CO or *CHO on Cu sites for further ethanol formation. For example, Cu63.9Au36.1 alloy key intermediate *CO or *CHO on Cu sites for further ethanol formation. For example, Cu63.9Au36.1 electrode, which was prepared through electrochemical deposition with a nanoporous Cu film as the alloy electrode, which was prepared through electrochemical deposition with a nanoporous Cu film template, produced ethanol with an FE of 12% at −0.41 V vs. RHE in 0.5 M KHCO3 [71]. By pulsed as the template, produced ethanol with an FE of 12% at −0.41 V vs. RHE in 0.5 M KHCO3 [71]. By electroreduction, ethanol was formed with a maximum FE of 25.5% over Cu55Ag45 alloy electrode pulsed electroreduction, ethanol was formed with a maximum FE of 25.5% over Cu55Ag45 alloy among the Cu-Ag alloys with different atomic ratios [72]. The key factors for the selective ethanol electrode among the Cu-Ag alloys with different atomic ratios [72]. The key factors for the selective production from CO2 are the formation of an oxide layer on Cu and desorption of intermediates on Ag ethanol production from CO2 are the formation of an oxide layer on Cu and desorption of under anodic bias. A kind of high-surface-area CuAg alloy wire was developed by electrodeposition intermediates on Ag under anodic bias. A kind of high-surface-area CuAg alloy wire was developed method with 3,5-diamino-1,2,4-triazole (DAT) as an inhibitor [73]. The alloy film containing 6% Ag by electrodeposition method with 3,5-diamino-1,2,4-triazole (DAT) as an inhibitor [73]. The alloy shows higher activity and selectivity for the electroreduction of CO2 to ethanol with FE of 25% in film containing 6% Ag shows higher activity and selectivity for the electroreduction of CO2 to comparison to the CuAg poly (20%) without adding the DAT inhibitor, at a cathode potential of −0.7 V ethanol with FE of 25% in comparison to the CuAg poly (20%) without adding the DAT inhibitor, at vs. RHE and a total current density of −300 mA·cm−2. The origin of the selective ethanol formation a cathode potential of −0.7 V vs. RHE and a total current density of −300 mA·cm-2. The origin of the is suggested to be the stabilization of Cu2O overlayer by CuAg wire and the optimal availability of selective ethanol formation is suggested to be the stabilization of Cu2O overlayer by CuAg wire and the CO intermediate due to the Ag incorporated in the alloy. Another kind of bimetallic Cu85Ag15 the optimal availability of the CO intermediate due to the Ag incorporated in the alloy. Another kind foam was synthesized by an additive (citrate)-assisted electrodeposition approach [74]. Such a foam structure enables the phase-segregation of Cu and Ag, and the well-despersed nano-sized Ag in thePDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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