Bimetallic In_(2)O_(3)/Bi_(2)O_(3) Catalysts Enable Highly Selective CO_(2) Electroreduction to Formate within Ultra-Broad Potential Windows

CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.

Electroreduction of CO_(2) to C_(2)H_(4) Regulated by Spacing Effect:Mechanistic Insights from DFT Studies

It is crucial to construct an efficient catalyst with high activity and excellent selectivity for realizing CO_(2) electroreduction reaction(CO_(2)ER)to high-value-added chemicals,especially the C2 products.Density functional theory(DFT)provides a powerful tool for investigating the promotional effect on C2 selectivity of finely tuned catalyst structures,which is currently difficult to control using experimental techniques,such as interatomic distances.In the work,5 Cu_(2)O catalyst models are constructed with different Cu-Cu atomic spacing(d_(Cu-Cu)).The results of DFT calculations show that adjusting the d_(Cu-Cu) can effectively tailor the electronic structures of active sites,enhance catalytic activity,and improve product selectivity.Specifically,the Cu atom pair spaced at d_(Cu-Cu)=2.5Åcould optimize the adsorption configuration of*CO and enhance the binding strength of*CO,thus improving*CO adsorption energy and reducing the energy barrier of C-C coupling.The work proves the feasibility of spacing effect in enhancing the C_(2)H_(4) selectivity of CO_(2) ER and provides a new idea for the catalyst modification for other reactions of polyprotons-coupled electrons.

Tandem catalysts CuSe/AuX for increasing local*CO concentration to promote the photocatalytic CO_(2) reduction to C_(2)H_(4)

It is highly desired yet challenging to strategically steer CO_(2) reduction reaction(CO_(2)RR)toward ethylene(C_(2)H_(4)) with high activity under visible light irradiation.The key to achieving this goal is increasing the local*CO concentration on the catalyst surface and promoting the C-C coupling progress.Here,we prepare tandem catalysts of CuSe/AuX to realize the photocatalytic reduction of CO_(2) to C_(2)H_(4) with high activity.Under light irradiation,the loaded Au NPs are used to activate and transfer CO_(2) to *CO.The generated*CO intermediate could migrate to the surface of CuSe and cause the C-C coupling process.Moreover,the theoretical calculation results show that the transport process of*CO from Au NPs to CuSe is spontaneous,which plays a critical role in guaranteeing the high concentration of *CO intermediate on the surface of CuSe.This work not only reveals the effect of tandem catalysis on CO_(2)RR to C2 products but also explores the most suitable tandem catalyst to produce C_(2)H_(4) with high activity by adjusting the loading amounts of Au NPs.Thus,it provides a way to adjust the Cu-based catalyst used in the production of C2 products by photocatalytic CO_(2)RR,which may attract extensive attention in the field.