Initial CO electroreduction into CO and its subsequent electroreduction pathways were selected to study the effect of specifically adsorbed halide anions X (X = F, Cl, Br, I) on CO electroreduction activity and product selectivity at Cu(111)/HO interfaces DFT calculations. The calculated results show that the presence of halide anions can exert a notable effect on the CO adsorption characteristics and that chemically adsorbed CO molecules can be formed. Furthermore, the halide-anion-modified Cu(111)/HO interfaces could significantly enhance the initial CO electroreduction into CO activity, which is regarded as the rate-determining step during CO electroreduction at clean Cu(111)/HO interfaces. Analysis of the initial CO electroreduction and Volmer reaction pathways showed that the halide-anion-modified Cu(111)/HO interfaces could suppress the HER and thus improve the CO electroreduction activity and product selectivity. It is speculated that the enhanced initial CO electroreduction activity at the F-, Cl-, Br-, and I-modified Cu(111)/HO interfaces may originate from the decreased work functions and anion radical CO formations. Simultaneously, we concluded that dimer OCCO formations in the presence of halide anions were more favorable than CHO during CO electroreduction according to the order of I > Br > Cl > F and could result in the production of C product, suggesting an improved CO electroreduction product selectivity. The present analyses of electronic structure may explain the more favorable OCCO formations in the order of I > Br > Cl > F. The present understanding of this effect will provide an improved scientific guideline for the control of CO electroreduction pathways and design of more efficient electrocatalysts.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d3cp01900d | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Transient pulsed discharge preparation of graphene aerogel supports asymmetric Cu cluster catalysts promote CO electroreduction.
Nat Commun
January 2025
School of Mechatronical Engineering, Beijing Institute of Technology, Beijing, 100081, China.
Designing asymmetrical structures is an effective strategy to optimize metallic catalysts for electrochemical carbon dioxide reduction reactions. Herein, we demonstrate a transient pulsed discharge method for instantaneously constructing graphene-aerogel supports asymmetric copper nanocluster catalysts. This process induces the convergence of copper atoms decomposed by copper chloride onto graphene originating from the intense current pulse and high temperature.
View Article and Find Full Text PDFEnantioselective reductive cross-couplings to forge C(sp)-C(sp) bonds by merging electrochemistry with nickel catalysis.
Nat Commun
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.
Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability.
View Article and Find Full Text PDFThe Proximal Protonation Source in Cu-NHx-C Single Atom Catalysts Selectively Boosts CO2 to Methane Electroreduction.
Angew Chem Int Ed Engl
January 2025
Peking University Shenzhen Graduate School, Shool of Chemical Biology and Biotechnology, Lishui Road, Nanshan District, -, Shenzhen, CHINA.
Regulating the coordination environment of active sites has proved powerful for tapping into their catalytic activity and selectivity in homogeneous catalysis, yet the heterogeneous nature of copper single-atom catalysts (SACs) makes it challenging. This work reports a bottom-up approach to construct a SAC (rGO@Cu-N(Hx)-C) by inlaying preformed amine coordinated Cu2+ units into reduced graphene oxide (rGO), permitting molecular level revelation on how the proximal N-site functional groups (N-H or N-CH3) impact on the carbon dioxide reduction reaction (CO2RR). It is demonstrated that the N-H moiety of rGO@Cu-NHx-C can serve as an in-situ protonation agent to accelerate the CO2-to-methane reduction kinetics, delivering a methane current density (163 mA/cm2) 2.
View Article and Find Full Text PDFEffect of Elemental Iron Containing Bauxite Residue Obtained After Electroreduction on High-Pressure Alkaline Leaching of Boehmitic Bauxite and Subsequent Thickening Rate.
Materials (Basel)
January 2025
Laboratory of Sorption Methods, Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences, 119991 Moscow, Russia.
The use of reduction leaching in the production of alumina from bauxite by the Bayer process in order to decrease the amount of waste (bauxite residue) by adding elemental iron or aluminum, as well as Fe salts and organic compounds in the stage of high-pressure leaching, requires the purchase of relatively expensive reagents in large quantities. The aim of this study was to investigate the possibility of the use of electrolytically reduced bauxite residue (BR) as a substitute for these reagents. Reduced BR was obtained from Al-goethite containing BR using a bulk cathode in alkaline suspension.
View Article and Find Full Text PDFRevealing catalyst restructuring and composition during nitrate electroreduction through correlated operando microscopy and spectroscopy.
Nat Mater
January 2025
Department of Interface Science, Fritz-Haber Institute of the Max-Planck Society, Berlin, Germany.
Electrocatalysts alter their structure and composition during reaction, which can in turn create new active/selective phases. Identifying these changes is crucial for determining how morphology controls catalytic properties but the mechanisms by which operating conditions shape the catalyst's working state are not yet fully understood. In this study, we show using correlated operando microscopy and spectroscopy that as well-defined CuO cubes evolve under electrochemical nitrate reduction reaction conditions, distinct catalyst motifs are formed depending on the applied potential and the chemical environment.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!