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Catalysts 2020, 10, 1287 3 of 25 2. Basic Principles of Clean Fuel Ethanol Production from CO2 Catalysts 2020, 10, x FOR PEER REVIEW 3 of 25 2.1. CO2 Electroreduction ElectroreductionofCO2 iscommonlycarriedoutinagas-tight,two-compartmentelectrolysis 2 cell equipped with a working electrode, a counter electrode and a proton exchange membrane as the separator(S(Scchheemee2A2A).)T.hTehmeemebmrabnreawneaswemaspelomypedlotyoerdestoricrtetshterictrtanthsepotrtaonfslpiqourtidopfhlaiqsueipdropdhuacstes fprroomdutchteswfromrkitnhgeweleocrtkriondgeetloecthroedceotuonthereecloeucntrtoedrelwechtreordeethwehyecraenthbeeyocxaindibzedox[i1d7i]z.edPr[i1o7r].toPrtihoer etoxpthereimexepnetrsi,mtheenatsp,pthliedapgpasli-etidghgtase-lteicgthrotleylseicstcroellyshisocuelldl sbheovualcdubuemveadcuanudmtehdenanpdurtghedn wpuitrhgeCdOwfitohr 2 3C0Om2 ifnorto3r0eamchinatcoonresatacnhtapHcovnasltuaentofptHhevealelucterolfyteh.eTehlecrterdoulyctieo.nTrheeacrteiodnucotfioCnOreiascctoionnduocfteCdOa2nids 2 mcoenadsucrteedbayncdycmliecavsoulrteadmbmyetcryclaicndvoplotatemnmtioestrtaytiacnedlepctortoelnytsiiossatat tfiicxedlepctortoelnytsiaslsa.t Tfihxedgapseooteunstiaanlsd. lTiqhueigdapsreoduuscatns darleiqgueinderparlolyduquctasnatirfieegdebnyeralglyasqcuharnotmifaietdogbryapahgaansdcahrnoumclaetaorgmraapghneatnicdraesnouncalnecaer (mNaMgnRe)tiscpercetsronmanetcer (oNr Ma lRiq)usipdechtromeateorgroarpahyl,iqreusipdecthirvoemly.atTohgerafparhayd,ariecsepffiectiievnecly.(FTEh)e, wfahraicdhaics defeffiicniendcays(tFhEe)p,werhceicnhtaigsedoefienledctraosntshceopnesrucmenetdagfoerotfhelefocrtrmoantsiocnonosfuamgeivdefnoprrtohdeufoctr,mcantiobnecoaflacugliavtedn apsrofodlulocwt,sca[n18b]ecalculatedasfollows[18] αnF FE = = Q where α is the quantity of transferred electrons for CO2 reduction to a given product; n is the number where α is the quantity of transferred electrons for CO2 reduction to a give−n1product; n is the number of moles for a desired product; F is the Faraday’s constant (96485 C·mol ) and Q (A·s) is the total of moles for a desired product; F is the Faraday’s constant (96485 C·mol−1) and Q (A·s) is the total quantity of charge passed. quantity of charge passed. Scheme 2. Illustrations of (A) H-cell configuration with a catalyst deposited on a solid substrate, Scheme 2. Illustrations of (A) H-cell configuration with a catalyst deposited on a solid substrate, (B) (B) flow cell configuration with a catalyst deposited on gas-diffusion electrode (GDE) and a flowing flow cell configuration with a catalyst deposited on gas-diffusion electrode (GDE) and a flowing catholyte channel, (C) GDE architecture and its 3-phase interface mechanism, (D) the working electrode catholyte channel, (C) GDE architecture and its 3-phase interface mechanism, (D) the working architecture in H-cell and its 2-phase interface mechanism for electrocatalytic CO2 reduction.. electrode architecture in H-cell and its 2-phase interface mechanism for electrocatalytic CO2 reduction.. Electroreduction of CO2 is a multi-step reaction process involving multiple electron transfer, and generally takes place at the electrode/electrolyte interface for the heterogeneous electrocatalysts [19]. Electroreduction of CO2 is a multi-step reaction process involving multiple electron transfer, It experiences such a process involving three major steps of chemical adsorption of CO2 on the surface and generally takes place at the electrode/electrolyte interface for the heterogeneous electrocatalysts of electrocatalysts, activation of CO2 to cleave C=O bonds and form C-O or C-H bonds through electron [19]. It experiences such a process involving three major steps of chemical adsorption of CO2 on the and/or proton transfer, and desorption of products from electrocatalysts surface after configuration surface of electrocatalysts, activation of CO2 to cleave C=O bonds and form C-O or C-H bonds rearrangement [18]. The applied electrocatalysts and electrolysis potentials significantly affect the final through electron and/or proton transfer, and desorption of products from electrocatalysts surface reduction products that may vary in the carbon compounds of CO, methane, formic acid, ethylene, after configuration rearrangement [18]. The applied electrocatalysts and electrolysis potentials methanol, ethanol, etc., or a mixture of them. This kind of dependence on electrocatalysts and significantly affect the final reduction products that may vary in the carbon compounds of CO, electrolysis potentials is ascribed to the different thermodynamic equilibrium potentials of these methane, formic acid, ethylene, methanol, ethanol, etc., or a mixture of them. This kind of products from CO2 reduction, as displayed in Table 1 [20]. From the view of thermodynamics, dependence on electrocatalysts and electrolysis potentials is ascribed to the different the equilibrium potentials around −0.2 to −0.6 V (versus normal hydrogen electrode (NHE), pH thermodynamic equilibrium potentials of these products from CO2 reduction, as displayed in Table = 7.0) of CO2 reduction are comparable to that of hydrogen evolution reaction (HER) (−0.41 V, 1 [20]. From the view of thermodynamics, the equilibrium potentials around −0.2 to −0.6 V (versus Table 1) [4]. That is why H2 is the major side-product during CO2 electroreduction in aqueous normal hydrogen electrode (NHE), pH = 7.0) of CO2 reduction are comparable to that of hydrogen evolution reaction (HER) (−0.41 V, Table 1) [4]. That is why H2 is the major side-product during CO2 electroreduction in aqueous electrolytes. Additionally, the very small differences between the thermodynamic potentials for CO2 reduction products bring about a challenge to selectively produce the desirable carbon compounds. Actually, the required potentials to drive CO2 reductions are morePDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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