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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Journal ArticleDOI
A Conductive Dinuclear Cuprous Complex Mimicking the Active Edge Site of the Copper(100)/(111) Plane for Selective Electroreduction of CO 2 to C 2 H 4 at Industrial Current Density
TL;DR: In this paper , a conductive dinuclear cuprous complex with a short intramolecular Cu···Cu contact for the electroreduction of CO-C coupling was reported.
Journal ArticleDOI
Single-site decorated copper enables energy- and carbon-efficient CO2 methanation in acidic conditions
Mengyang Fan,Rui Kai Miao,Pengfei Ou,Yi Xu,Zih-Yi Lin,Tsung-Ju Lee,Sung Fu Hung,Ke Xie,Jianan Erick Huang,Wei-quan Ni,Jun Li,Adnan Ozden,Colin O’Brien,Yuanjun Chen,Yurou Celine Xiao,Shijie Liu,Joshua Wicks,Xue Wang,Jehad Abed,Erfan Shirzadi,Edward H. Sargent,David Sinton +21 more
TL;DR: In this article , a CH4-selective electrocatalysis in acidic conditions via a coordination method was pursued, stabilizing free Cu ions by bonding Cu with multidentate donor sites.
Journal ArticleDOI
An unusual zig-zag 2D copper(I) coordination polymer as an outstanding catalyst for azide-alkyne "click" chemistry at room temperature.
Mehmet B. Bilgic,Azra Kocaarslan,Kerem Kaya,Armağan Atsay,Erik Svensson Grape,Jianhong Chen,Yusuf Yagci +6 more
TL;DR: In this paper , a two-dimensional (2D) new copper coordination polymer, namely Cu(bzpdc), containing the ligand benzophenone 4,4'-dicarboxylate, and its effective use as catalyst for the azide-alkyne click chemistry at room temperature is reported.
Journal ArticleDOI
Assembling Metal Organic Layer Composites for High‐Performance Electrocatalytic CO 2 Reduction to Formate
TL;DR: In this article , a freestanding metal-organic layer (MOL) with a 2D kgd (kagome dual) lattice was constructed with abundant surface oxygenate groups serving as anchoring sites to immobilize diverse guests.
Journal ArticleDOI
Electrochemical CO2 reduction with ionic liquids: Reviewing and evaluating
Yangshuo Li,Xiaoyan Ji,Fangfang Li,Aatto Laaksonen,Chuan Wang,Paul Cobden,Per Boden,Yanrong Liu,Xiangping Zhang +8 more
TL;DR: The increasing CO2 emission as the chief culprit causing many environmental problems could be addressed via electrochemical CO2 reduction (CO2R) to the added-value carbon-based chemicals as mentioned in this paper .
References
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Journal ArticleDOI
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
Yan Zhao,Donald G. Truhlar +1 more
TL;DR: The M06-2X meta-exchange correlation function is proposed in this paper, which is parametrized including both transition metals and nonmetals, and is a high-non-locality functional with double the amount of nonlocal exchange.
Journal ArticleDOI
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
P. Jeffrey Hay,Willard R. Wadt +1 more
TL;DR: In this article, effective core potentials (ECP) have been derived to replace the innermost core electron for third row (K), fourth row (Rb-Ag), and fifth row (Cs-Au) atoms.
Journal ArticleDOI
Quantum mechanical continuum solvation models.
TL;DR: This paper presents a meta-modelling procedure called "Continuum Methods within MD and MC Simulations 3072", which automates the very labor-intensive and therefore time-heavy and expensive process of integrating discrete and continuous components into a discrete-time model.
Journal ArticleDOI
Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules
TL;DR: In this article, an extended basis set of atomic functions expressed as fixed linear combinations of Gaussian functions is presented for hydrogen and the first row atoms carbon to fluorine, where each inner shell is represented by a single basis function taken as a sum of four Gaussians and each valence orbital is split into inner and outer parts described by three and one Gaussian function, respectively.
Journal ArticleDOI
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
Kyo Sung Park,Zheng Ni,Adrien P. Côté,Jae Yong Choi,Rudan Huang,Fernando J. Uribe-Romo,Hee K. Chae,Michael O'Keeffe,Omar M. Yaghi +8 more
TL;DR: Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvents.
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