Synthesis of a Boron–Imidazolate Framework Nanosheet with Dimer Copper Units for CO₂ Electroreduction to Ethylene

Abstract

Fundamental understanding of the dependence between the structure and composition on the electrochemical CO 2 reduction reaction (CO 2 RR) would guide the rational design of highly efficient and selective electrocatalysts.Amajor impediment to the deep reduction CO 2 to multi-carbon products is the complexity of carbon-carbon bond coupling. The chemically well-defined catalysts with atomically dispersed dual-metal sites are required for these CÀCc oupling involved processes.H ere,w ed eveloped ac atalyst (BIF-102NSs) that features Cl À bridged dimer copper (Cu 2 )u nits, which delivers high catalytic activity and selectivity for C 2 H 4 . Mechanistic investigation verifies that neighboring Cu monomers not only perform as regulator for varying the reaction barrier,b ut also affordd istinct reaction paths compared with isolated monomers,r esulting in greatly improved electroreduction performance for CO 2 .

Predesign of Catalytically Active Sites via Stable Coordination Cluster Model System for Electroreduction of CO2 to Ethylene

“…Although the FE C 2 H 4 of Cu 3 -X are lower than that of the most superior CO 2 RR electrocatalysts (e.g., nanomaterials) reported so far, the precise structure-property relationship built by this crystalline model system can provide more insights into reaction mechanism for electrochemical CO 2 -to-C 2 H 4 conversion and the future design of more efficient electrocatalysts.M oreover,i td eserves to be mentioned that the electrocatalytic performance of Cu 3 -Br is comparable to those of the best-performing stable metal-organic complex electrocatalysts reported so far (Figure 3d and Table S8). [3,14] Compared with the electrocatalysts reported by our group recently,t he Cu 3 -Br could give FE C 2 H 4 of 55.01 %a talower potential (À0.7 V) and keep the selectivity basically unchanged in awide potential range (À0.7 VtoÀ1.1 V). [3c] It is noteworthy that the main competitive product of C 2 H 4 is CO rather than H 2 when the CO 2 RR is catalyzed by Cu 3 -X, particularly the FE H 2 can be controlled below 15 %, which means an important progress in the selectivity control of CO 2 RR in aqueous solution.…”

“…[2] Therefore,i th as been aq uite important but challenging goal in the field of electrochemical CO 2 reduction reaction (CO 2 RR) to construct the welldefined electrocatalysts for the conversion of CO 2 to C 2 H 4 with high selectivity and efficiency. [3] In recent years,copperbased materials have been widely accepted as efficient catalysts for electrocatalytic reduction of CO 2 to C 2 H 4 . [4] Furthermore,alarge number of tailoring strategies,including crystalline faceting, [5] multimetallic alloying, [6] multicomponent doping [7] and morphology controlling, [8] etc.,h ave been applied to Cu-based catalysts to improve their activity and selectivity for electrochemical conversion of CO 2 to C 2 H 4 .…”

Hydroxy‐Group‐Functionalized Single Crystal of Copper(II)‐Porphyrin Complex for Electroreduction CO2 to CH4

“…The FE C 2 H 4 is maintained above 11.7 % from À 1.3 to À 1.5 V (Figure 3c), which is similar to the performance of previous copper porphyrin-based catalysts [24,27] and higher than that of copper-based boron imidazolate frameworks. [35] The only detected liquid product is formic acid, and the FEs are < 2 % at the applied potentials (Figure S12). Strikingly, CH 4 becomes the main product over other carbon products with the potential increase and the FE CH 4 achieves a maximum value of 51.3 % at À 1.5 V. Meanwhile, FE CO and FE C 2 H 4 are 5.2 and 11.7 % at the same potential, respectively.…”

Atomic Bridging Structure of Nickel–Nitrogen–Carbon for Highly Efficient Electrocatalytic Reduction of CO2

“…[4a, 6] To tackle this challenge, developing new catalytic sites consisting of two adjacent active metal atoms with exposed atomic interfaces and synergistic interactions would be an effective way to increase catalytic activity. [7] For instance, the dual-atom Ag site is able to promote CO 2 adsorption and subsequently stabilize the intermediates by reducing the formation energy barrier of the intermediate for the enhanced performance in comparison with singleatom Ag sites. [7b] Furthermore, it has been proposed that MÀ N x À C sites with different coordination numbers (e.g., NiÀ N 2 À C) are of importance in changing the atomic structure of the bridging atoms and the surface charge status, which plays a vital role in modulating the electrocatalytic performance.…”