Molybdenum–Bismuth Bimetallic Chalcogenide Nanosheets for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Methanol

Abstract

Methanol is av ery useful platform molecule and liquid fuel. Electrocatalytic reduction of CO 2 to methanol is apromising route,whichcurrently suffers from low efficiency and poor selectivity.H erein we report the first work to use aM o-Bi bimetallic chalcogenide (BMC) as an electrocatalyst for CO 2 reduction. By using the Mo-Bi BMC on carbon paper as the electrode and 1-butyl-3-methylimidazolium tetrafluoroborate in MeCN as the electrolyte,t he Faradaic efficiency of methanol could reach 71.2 %w ith ac urrent density of 12.1 mA cm À2 ,w hichi sm uchh igher than the best result reported to date.T he superior performance of the electrode resulted from the excellent synergistic effect of Mo and Bi for producing methanol. The reaction mechanism was proposed and the reason for the synergistic effect of Mo and Bi was discussed on the basis of some control experiments.This work opens away to produce methanol efficiently by electrochemical reduction of CO 2 .CO 2 is acheap,abundant, and safe carbon resource,and its transformation into valuable chemicals and fuel has received much attention.[1,2] CO 2 conversion can be achieved by chemical methods,e lectrochemical reduction, and photocatalytic reduction. [3,4] Theelectrochemical reaction system is compact, modular, and the efficiencycan be easily controlled by different parameters,s uch as electrode materials,e lectrolytes,and applied potentials.[5] Theelectrochemical reduction of CO 2 can proceed through two-, four-, six-, and eightelectron reduction pathways in different electrolytes over metals,metal complexes,and non-metallic electrodes,and the major products are CO, [6][7][8][9] formic acid/formate,

Fundamentals and Challenges of Electrochemical CO2 Reduction Using Two-Dimensional Materials

“…However, using 2D nanosheets for ECR selectively to CH 3 OH has been rarely reported. Han and colleagues 81 showed that Mo-Bi bimetallic chalcogenide (BMC) nanosheets were able to reduce CO 2 to CH 3 OH with a faradic efficiency of 71.2% and a current density of 12.1 mA cm À2 , which outperform earlier reported catalysts. In contrast, CH 3 OH was not generated when bulk MoS 2 /carbon paper (CP) or Bi 2 S 3 /CP electrode was used.…”

Aqueous Electrochemical Reduction of Carbon Dioxide and Carbon Monoxide into Methanol with Cobalt Phthalocyanine

“…The electrochemical reduction of carbon dioxide (CO 2 )into methanol (CH 3 OH) is considered as amajor target that could enable at ransition from fossil fuels to renewable fuels.T o catalyze the six-electron-six-proton reduction of CO 2 to CH 3 OH, efforts have been devoted to the use of metal oxides,m etal alloys,o rc halcogenide-based catalytic electrodes. [1][2][3][4] Most of these materials either require the use of rare metals,o ra re not selective for methanol because they cogenerate more reduced products (for example,methane or C 2 molecules). [5,6] Additionally,t he thermodynamic stability window of metal oxides is limited [7] and the reduced metal electrodes typically have low activity for CH 3 OH produc-tion, [8] leading to performance instability.O ne promising strategy to achieve high selectivity is to use molecular catalysts to precisely control the structure of the active site.…”

Bismuth coated graphite felt modified by silver particles for selective electroreduction of CO2 into formate in a flow cell

“…The average total surface current density measured for Ag-Bi@GF reached 76 and 107 mA cm -2 at -1.6 and -1.8 V SCE , respectively (Fig. 9), which is very promising for a CO 2 -saturated solution at atmospheric pressure [21][22][23] although the value is lower than the critical one usually admitted for practical applications [26].…”

“…An increase in FE has been obtained with Cu-Bi electrodes, which was attributed to a change in the local environment of Bi modulated by Cu atoms [21]. A synergistic effect has also been observed between Bi and Mo for producing methanol [23]. S-O composite involving a bimetallic Ag-Bi system has also improved Faradaic efficiency for the selective CO 2 reduction into formate.…”

“…In that context, Ag has been associated to Cu in order to improve the catalytic performance for CO 2 reduction due to a tandem sequential catalysis and electronic effect [19,20]. Bimetallic electrodes containing Bi have also been studied [21][22][23][24][25].…”