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
Reads0
Chats0
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
Citations
More filters
Journal ArticleDOI
Grain Boundary and Interface Interaction Co-regulation Promotes SnO2 Quantum Dots for Efficient CO2 Reduction
TL;DR: In this paper , a simple low-cost, green method as an electrocatalyst for CO 2 reduction was proposed. And the obtained SnO 2 /NC exhibits high electrocatalytic performance for conversion of CO 2 to formate with high selectivity.
Journal ArticleDOI
Electrocatalytic CO2 Reduction and H2 Evolution by a Copper (II) Complex with Redox-Active Ligand
Jingqing Li,Shi‐fu Zhang,Jinmiao Wang,Xiao-Feng Yin,Z. B. Han,Guofen Chen,Dong-Mei Zhang,Mei Wang +7 more
TL;DR: In this article , a copper (II) complex with redox-active ligand [Cu(L1)2NO3]NO3 (1, L1 = 2-(6-methoxypyridin-2-yl)-6-nitro-1h-benzo [D] imidazole) was developed, and X-ray crystallography reveals that the Cu ion in cation of complex 1 is coordinated by two redox ligands L1 and one labile nitrate ligand, which could assist the metal center for catalysis.
Journal ArticleDOI
A Special Bi-S Motif Catalyst for Highly Selective CO2 Conversion to Methanol
TL;DR: Li et al. as discussed by the authors developed an in-situ sulfurizing strategy over the Bi-based metal-organic frameworks (Bi-BTC ) and disperse stable and special Bi-S motif on subsequent S-doped carbon-framework (called BS@Cx ).
Journal ArticleDOI
Atomically Dispersed CuNx Sites from Thermal Activation of Boron Imidazolate Cages for Electrocatalytic Methane Generation
Soumyodip Banerjee,Justin M. Gorham,Pilar Beccar-Varela,H. G. Hackbarth,Maxime A. Siegler,Natalia Drichko,Joshua Wright,Nicholas M. Bedford,V. Sara Thoi +8 more
TL;DR: In this paper , the copper boron imidazolate cage, BIF-29(Cu), was used as a precursor for nitrogen coordinated single site catalysts for CO 2 RR.
Journal ArticleDOI
Sulfonated covalent organic framework packed nafion membrane with high proton conductivity for H2/O2 fuel cell applications
Zhichao Shao,Xiaojing Xue,Kexin Gao,Junshuai Chen,Li-Xiang Zhai,Tianyang Wen,Shenglin Xiong,Hongwei Hou,Liwei Mi +8 more
TL;DR: In this paper , a multichannel proton conduction membrane constructed from a 2D COF (ZUT-COF-SO3H) is presented, which has low activation energy and high performance.
References
More filters
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.
Related Papers (5)
Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte
Stephanie A. Nitopi,Erlend Bertheussen,Søren Bertelsen Scott,Xinyan Liu,Albert K. Engstfeld,Albert K. Engstfeld,Sebastian Horch,Brian Seger,Ifan E. L. Stephens,Ifan E. L. Stephens,Karen Chan,Karen Chan,Christopher Hahn,Christopher Hahn,Jens K. Nørskov,Jens K. Nørskov,Jens K. Nørskov,Thomas F. Jaramillo,Thomas F. Jaramillo,Ib Chorkendorff +19 more