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Catalysts 2020, 10, x FOR PEER REVIEW 11 of 25 intermediates formed in situ, which, in turn, covers the local catalyst surface and thereby stabilized Cu+ species [60]. At the potential of −0.61 V vs. RHE in 2 M KOH, this catalyst yields a maximum Catalysts 2020, 10, 1287 11 of 25 ethanol FE of 27% and delivers a high current density of −320 mA·cm-2 in a flow cell system (Figure 4). Figure4..((A))TEM-E-EDXXeleelmemenentatlamlmapapipnigngofomfumltuihltoihllolwlo,wso,lisdolaidndafnrdagfmraegnmtCenutOCus2aOmspalems.p(lBes).F(EBs) 2 oFfECsOofCreOd2ucretidouncmtioanjormparjordupcrtosdounctmsuolnti-mhoulltoi-whoClluowOC.(uC2)OC.(C/)CC2p+/rCod1upcrtosdeuleccttsivelietyctoivnittyheonthrthee 2 2 2+1 tyhpreesotyfpcaetsaloyfstcsa.tRaleypsrtosd.uRceepdrowdiuthcepderwmitshsiopner[m60i]s.siCoonpy[6r0ig].htC2o0p2y0r,iAghmte2r0ic2a0n,CAhmemericalnSoCchietmy.ical Society. Besides, the incorporation of heteroatoms into catalysts is another efficient approach to stabilized Cu+speciesandpromoteCO electroreduction.IntroducingNintoCutoformCuN,whenasthe Besides, the incorporatio2n of heteroatoms into catalysts is another efficie3nt approach to support of Cu+ catalyst, showed the enhanced FE (around 19%) for ethanol, which results from the stabilized Cu species and promote CO2 electroreduction. Introducing N into Cu to form Cu3N, stabilized Cu+ by N in the Cu N structure [61]. A B-doped oxide-derived-Cu has been reported to when as the support of Cu cata3lyst, showed the enhanced FE (around 19%) for ethanol, which results promoteCformationw+ithahigherFaradaiceffiencicy(20%)thanthatofOD-Cu(12%),duetothe from the s2tabilized Cu by N in the Cu3N structure [61]. A B-doped oxide-derived-Cu has been Cu+ species stabilized by the introduction of B [62]. It has also been reported that B can be used reported to promote C2 formation with a higher Faradaic effiencicy (20%) than that of OD-Cu (12%), to tune the loc+al electronic structure of Cu with positive valence sites, which results in boosting the due to the Cu species stabilized by the introduction of B [62]. It has also been reported that B can be ethanol formation with a high FE of 27% at −1.1 V vs. RHE in 0.1 M KCl [63]. By incorporating used to tune the local electronic structure of Cu with positive valence sites, which results in boosting sulfur atoms in the catalyst core, and Cu vacancies in its shell, Sargent and his co-workers realized the ethanol formation with a high FE of 27% at −1.1 V vs. RHE in 0.1 M KCl [63]. By incorporating CuS-Cu-Vcore-shellnanoparticlesthatenhanceCO reductiontoethanolwithahighFEof25%ina sul2fur atoms in the catalyst core, and Cu vacancies 2in its shell, Sargent and his co-workers realized flow cell [64]. In a recent report, F atoms in the F-modified Cu catalyst facilitate the increase in Cu+ Cu2S-Cu-V core-shell nanoparticles that enhance CO2 reduction to ethanol with a high FE of 25% in a sites and keeps them unchanged during long-term CO reduction [65]. Thus, a FE of 16% towards+ flow cell [64]. In a recent report, F atoms in the F-modif2ied Cu catalyst facilitate the increase in Cu ethanol was achieved at −800 mA·cm−2 (−0.54 V vs. RHE) in a flow cell system. By increasing surface sites and keeps them unchanged during long-term CO2 reduction [65]. Thus, a FE of 16% towards Cu+ sites, the modification of F also p-2romotes H O activation to *H species, CO adsorption and the ethanol was achieved at −800 mA·cm (−0.54 V v2s. RHE) in a flow cell system. By increasing surface hyd+rogenationof*COtoa*CHOintermediatethatcanreadilyundergocoupling. Cu sites, the modification of F also promotes H2O activation to *H species, CO adsorption and the In order to accelerate H O dissociation to *H species and change the H adsorption energy on hydrogenation of *CO to a *C2HO intermediate that can readily undergo coupling. Cu, Sargent’s group reported a complementary approach of hydroxide doping to tune the *H species In order to accelerate H2O dissociation to *H species and change the H adsorption energy on Cu, on Cu [66]. The enhanced *H coverage easily attacks the *HCCOH, forming *HCCHOH, the key Sargent’s group reported a complementary approach of hydroxide doping to tune the *H species on intermediate towards ethanol. Hence, the most efficient Ce(OH) -doped-Cu catalyst exhibits a high Cu [66]. The enhanced *H coverage easily attacks the *HCCxOH, forming *HCCHOH, the key ethanol FE of 43% and a partial current density of −128 mA·cm−2 in a flow cell. intermediate towards ethanol. Hence, the most efficient Ce(OH)x-doped-Cu catalyst exhibits a high Bridging homogeneous molecular systems to tune heterog−e2neous catalysts has been considered ethanol FE of 43% and a partial current density of −128 mA·cm in a flow cell. a promising approach for the development of new electrodes, combining the advantages of both Bridging homogeneous molecular systems to tune heterogeneous catalysts has been considered approaches [88]. When organic molecules or metal complexes are adjacent to heterogeneous active sites, a promising approach for the development of new electrodes, combining the advantages of both the binding interactions may tune the stability of intermediates, and improve catalytic performance approaches [88]. When organic molecules or metal complexes are adjacent to heterogeneous active by increasing ethanol FE as well as decreasing overpotential. An good example of this bridge is sites, the binding interactions may tune the stability of intermediates, and improve catalytic N-substituted pyridinium additives, which are able to form a deposited film on polycrystalline Cu performance by increasing ethanol FE as well as decreasing overpotential. An good example of this electrodes upon reduction, tuning the selectivity of ethanol formation [67]. A maximum ethanol FE bridge is N-substituted pyridinium additives, which are able to form a deposited film on 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. Besides this, a nanostructured CuPDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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