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ArticleCathodic Corrosion-Induced Structural Evolution of CuNi Electrocatalysts for Enhanced CO2 ReductionWenjin Sun 1,†, Bokki Min 2,†, Maoyu Wang 3, Xue Han 4, Qiang Gao 1, Sooyeon Hwang 5, Hua Zhou 3, and Huiyuan Zhu 1,2,*1 Department of Chemistry, University of Virginia, Charlottesville, VA 22904, USA2 Department of Chemical Engineering, University of Virginia, Charlottesville, VA 22904, USA3 Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439, USA4 Department of Chemical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA5 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973, USA* Correspondence: kkx8js@virginia.com† These authors contributed equally to this work.Received: 22 October 2024; Revised: 25 November 2024; Accepted: 27 November 2024; Published: 4 December 2024 Abstract: The electrochemical CO2 reduction reaction (CO2RR) has attracted significant attention as a promising strategy for storing intermittent energy in chemical bonds while sustainably producing value-added chemicals and fuels. Copper-based bimetallic catalysts are particularly appealing for CO2RR due to their unique ability to generate multi-carbon products. While substantial effort has been devoted to developing new catalysts, the evolution of bimetallic systems under operational conditions remains underexplored. In this work, we synthesized a series of CuxNi1−x nanoparticles and investigated their structural evolution during CO2RR. Due to the higher oxophilicity of Ni compared to Cu, the particles tend to become Ni-enriched at the surface upon air exposure, promoting the competing hydrogen evolution reaction (HER). At negative activation potentials, cathodic corrosion has been observed in CuxNi1−x nanoparticles, leading to the significant Ni loss and the formation of irregularly shaped Cu nanoparticles with increased defects. This structural evolution, driven by cathodic corrosion, shifts the electrolysis from HER toward CO2 reduction, significantly enhancing the Faradaic efficiency of multi-carbon products (C2+).
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This content will become publicly available on January 10, 2026
Size-Controlled Synthesis of Rhodium Nanocatalysts and Applications in Low-Temperature Hydroformylation
ArticleSize-Controlled Synthesis of Rhodium Nanocatalysts and Applications in Low-Temperature HydroformylationAndrew Lamkins 1,2, Charles J. Ward 1,2, Jeffrey T. Miller 3, Ziad Alsudairy 4, Xinle Li 4, Joseph Thuma 1,2, Ruoyu Cui 1,2, Xun Wu 1,2, Levi M. Stanley 1 and Wenyu Huang 1,2,*1 Department of Chemistry, Iowa State University, Ames, IA 50010, USA2 Ames Laboratory, U.S. Department of Energy, Ames, IA 50010, USA3 Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA4 Department of Chemistry, Clark Atlanta University, Atlanta, GA 30314, USA* Correspondence: whuang@iastate.eduReceived: 3 December 2024; Revised: 30 December 2024; Accepted: 3 January 2025; Published: 10 January 2025 Abstract: Controlling the size and distribution of metal nanoparticles is one of the simplest methods of tuning the catalytic properties of a material. For a nanocrystal particle, the ratio of edge-to-terrace sites can be critical in determining its catalytic activity and selectivity to desired products. To study these effects, we have developed a simple impregnation method of controlling the dispersion of rhodium atoms at the same metal loading in the range of nanoparticles less than 10 nm. Rh precursor salts are loaded onto inert SBA-15, and increasing the ratio of chloride to acetylacetonate salts improves the dispersion of rhodium atoms to form small Rh nanoparticles. Extensive characterization of the size-controlled catalysts, including XAS and in-situ CO-DRIFTS studies, has been performed to characterize the structure of Rh nanoparticles. Applying these catalysts to the hydroformylation of styrene, we observed that turnover frequency increases with decreasing particle size from 6.4 to 1.6 nm. When applied to hydroformylation reactions, we achieved a high branched product selectivity and successfully demonstrated a route to synthesizing the pain relief drug ibuprofen. This simple method can also synthesize Pt and Pd nanoparticles between 2–10 nm.
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- Award ID(s):
- 2108307
- PAR ID:
- 10640501
- Publisher / Repository:
- Scilight
- Date Published:
- Journal Name:
- Materials and Interfaces
- ISSN:
- 2982-2394
- Page Range / eLocation ID:
- 1
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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