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Enhanced Cuprophilic Interactions in Crystalline Catalysts Facilitate the Highly Selective Electroreduction of CO2 to CH4.

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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.

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Citations
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Identifying the Optimal Oxidation State of Cu for Electrocatalytic CO2-to-C2+ Products

TL;DR: The electrocatalytic CO2 reduction reaction (CO2RR) to C2+ products is of great importance as discussed by the authors , and the co-operation of Cu1+ and Cu0 in the catalysts can yield high Faradaic...
Journal ArticleDOI

Electrocatalysis CO2 to Tunable Syngas upon Fe Clusters Catalyst Dispersed on Bamboo-like NCTs.

TL;DR: In this article , the authors reported a catalyst of Fe@NBCT with a high performance in electrocatalytic CO2 to syngas with tunable H2/CO ratio.
Journal ArticleDOI

Flexible Cuprous Triazolate Frameworks as Highly Stable and Efficient Electrocatalysts for CO2 Reduction with Tunable C2H4/CH4 Selectivity

TL;DR: In this article , flexible Cu(I) triazolate frameworks are reported as efficient, stable, and tunable electrocatalysts for CO2 reduction to C2H4/CH4.
Journal ArticleDOI

Achieving High-Efficient Photoelectrocatalytic Degradation of 4-Chlorophenol via Functional Reformation of Titanium-Oxo Clusters.

TL;DR: In this article , three stable titanium-oxo clusters (Ti10Ac6, Ti10Fc8, and Ti12Fc2Ac4) modified with a monofunctionalized ligand (9-anthracenecarboxylic acid (Ac) or ferrocenec-carboxyl acid (Fc)) and bifunctionalised ligands (Ac and Fc) were constructed to achieve very high PEC activity and degradation efficiency.
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