Journal ArticleDOI
Enhanced Cuprophilic Interactions in Crystalline Catalysts Facilitate the Highly Selective Electroreduction of CO2 to CH4.
Lei Zhang,Xiao-Xin Li,Zhongling Lang,Yang Liu,Jiang Liu,Lin Yuan,Wan-Yue Lu,Yuan-Sheng Xia,Long-Zhang Dong,Daqiang Yuan,Ya-Qian Lan,Ya-Qian Lan +11 more
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TLDR
In this paper, two stable copper(I)-based coordination polymer (NNU-32 and NNU-33(S)) catalysts are synthesized and integrated into a CO2 flow cell electrolyzer, which exhibited very high selectivity for electrocatalytic CO2-to-CH4 conversion due to clearly inherent intramolecular cuprophilic interactions.Abstract:
Cu(I)-based catalysts have proven to play an important role in the formation of specific hydrocarbon products from electrochemical carbon dioxide reduction reaction (CO2RR). However, it is difficult to understand the effect of intrinsic cuprophilic interactions inside the Cu(I) catalysts on the electrocatalytic mechanism and performance. Herein, two stable copper(I)-based coordination polymer (NNU-32 and NNU-33(S)) catalysts are synthesized and integrated into a CO2 flow cell electrolyzer, which exhibited very high selectivity for electrocatalytic CO2-to-CH4 conversion due to clearly inherent intramolecular cuprophilic interactions. Substitution of hydroxyl radicals for sulfate radicals during the electrocatalytic process results in an in situ dynamic crystal structure transition from NNU-33(S) to NNU-33(H), which further strengthens the cuprophilic interactions inside the catalyst structure. Consequently, NNU-33(H) with enhanced cuprophilic interactions shows an outstanding product (CH4) selectivity of 82% at -0.9 V (vs reversible hydrogen electrode, j = 391 mA cm-2), which represents the best crystalline catalyst for electrocatalytic CO2-to-CH4 conversion to date. Moreover, the detailed DFT calculations also prove that the cuprophilic interactions can effectively facilitate the electroreduction of CO2 to CH4 by decreasing the Gibbs free energy change of potential determining step (*H2COOH → *OCH2). Significantly, this work first explored the effect of intrinsic cuprophilic interactions of Cu(I)-based catalysts on the electrocatalytic performance of CO2RR and provides an important case study for designing more stable and efficient crystalline catalysts to reduce CO2 to high-value carbon products.read more
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Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis
TL;DR: In this paper , the most recent advances in synthesizing value-added chemicals by heterogeneous catalysis are summarized, and an overview of electrocatalytic oxidation and reduction processes as well as paired electrocatalysis is provided, and the anodic oxidation of alcohols (monohydric and polyhydric), aldehydes and amines are discussed.
Journal ArticleDOI
Metal-Organic framework catalysts: A versatile platform for bioinspired electrochemical conversion of carbon dioxide
TL;DR: In this paper , the most recent advances in developing MOF-based electrocatalysts for CO2 reduction are discussed, and various transformations and modifications that can be applied to MOFs to emphasize the versatility of these materials.
Journal ArticleDOI
Novel ultrabright luminescent copper nanoclusters and application in light-emitting devices.
TL;DR: In this article, two newly synthesized ultra-small copper nanoclusters, [Cu3(μ3-H)(μ2-dppy)4]-ClO4)2 (1) and [Cu4(μ4-H))(μ 2-dped)4(m2-Cl)2](ClO 4) (2) (dppy = diphenyl-2-pyridylphosphine), have been shown to exhibit ultrabright yellow and yellow-green room-temperature phosphorescence (RTP) emission,
Journal ArticleDOI
Dual-active sites design of Snx-Sby-O-GO nanosheets for enhancing electrochemical CO2 reduction via Sb-accelerating water activation
Haichuan He,Jian Wu,Xiaoxia Yu,Duan Xiao,Yan Wang,Fei Chen,Liqiang Wang,Linlin Wu,Jianhan Huang,Ning Zhao,Liu Deng,You-Nian Liu +11 more
TL;DR: In this article , a dual-active sites design of Snx-Sby-O-GO nanosheets (NSs) for controlling the reaction pathways was proposed.
Journal ArticleDOI
Structural and interfacial engineering of well-defined metal-organic ensembles for electrocatalytic carbon dioxide reduction
TL;DR: In this paper , a review of the fundamental electrochemistry of CO2RR and its evaluation criteria is presented, with emphasis on the engineering of metal centers and ligands, their interaction with supports, as well as in situ reconstruction of metal-organic ensembles.
References
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