Single-Atom Metal Anchored Zr₆-Cluster-Porphyrin Framework Hollow Nanocapsules with Ultrahigh Active-Center Density for Electrocatalytic CO₂ Reduction

Abstract

Designing earth-abundant electrocatalysts toward highly efficient CO 2 reduction has significant importance to decrease the global emission of greenhouse gas. Herein, we propose an efficient strategy to anchor non-noble metal single atoms on Zr 6 -cluster-porphyrin framework hollow nanocapsules with well-defined and abundant metal-N 4 porphyrin sites for efficient electrochemical CO 2 reduction. Among different transition metal single atoms (Mn, Fe, Co, Ni, and Cu), Co single-atom anchored Zr 6 -cluster-porphyrin framework hollow nanocapsules demonstrated the highest activity and selectivity for CO production. The rich Co−N 4 active centers and hierarchical porous structure contribute to enhanced CO 2 adsorption capability and moderate binding strength of reaction intermediates, thus facilitating *CO desorption and CO 2 -to-CO conversion. The Co-anchored nanocapsules maintain high efficiency and well-preserved stability during long-term electrocatalysis tests. Moreover, the Co-anchored nanocapsules exhibit a remarkable solar-to-CO energy conversion efficiency of 12.5% in an integrated solar-driven CO 2 reduction/O 2 evolution electrolysis system when powered by a custom large-area [Cs 0.05 (FA 0.85 MA 0.15 ) 0.95 ]Pb 0.9 (I 0.85 Br 0.15 ) 3 -based perovskite solar cell.

Rapid and Green Electric-Explosion Preparation of Spherical Indium Nanocrystals with Abundant Metal Defects for Highly-Selective CO2 Electroreduction

“…Electrochemical conversion of greenhouse gas CO 2 into high-value added chemicals powered by renewable electricity under ambient conditions provides a promising route to achieving a carbon-neutral future and mitigating a global climate crisis. − Previous literature reported that CO 2 can be reduced to various carbonous products (such as CO, , CH 4 , HCOOH, , ethylene, acetic acid, n-propanol, and so on) via electrochemical reaction paths. Among these products, HCOOH is broadly regarded as an ideal carrier molecule for hydrogen storage due to its easy access and high energy density. , However, the electrochemical CO 2 reduction reaction (CO 2 RR) is limited by high activation energy for the activation of thermodynamically stable CO 2 molecules and the competition of the hydrogen evolution reaction (HER) in aqueous solution. , Therefore, it is imperative to rationally design and construct advanced electrocatalysts with high activity and selectivity for the CO 2 RR.…”

“…E lectrochemical conversion of greenhouse gas CO 2 into high-value added chemicals powered by renewable electricity under ambient conditions provides a promising route to achieving a carbon-neutral future and mitigating a global climate crisis. 1−4 Previous literature reported that CO 2 can be reduced to various carbonous products (such as CO, 5,6 CH 4 , 7 HCOOH, 8,9 ethylene, 10 acetic acid, 11 n-propanol, 12 and so on) via electrochemical reaction paths. Among these products, HCOOH is broadly regarded as an ideal carrier molecule for hydrogen storage due to its easy access and high energy density.…”

Heat-treated copper phthalocyanine on carbon toward electrochemical CO2 conversion into ethylene boosted by oxygen reduction

“…2 The conversion of CO 2 into fuels is a highly promising approach to alleviate the environmental and energy crisis. 3 Compared with thermochemical, biochemical, and photocatalytic conversion, the electrochemical CO 2 RR has attracted more and more attention because of mild conditions, controllable reaction parameters, and the employment of renewable and off-peak electricity. 4,5 Intriguingly, the electrochemical CO 2 RR can produce C 2 H 4 , which is an important industrial chemical feedstock with a huge market demand and a high economic value.…”

Review on Electrocatalytic Coreduction of Carbon Dioxide and Nitrogenous Species for Urea Synthesis

“…Single atom catalysts have attracted more attention in heterogeneous catalysis conversion reactions such as electrochemical CO 2 reduction, − N 2 reduction, ,, O 2 reduction, − and H 2 O decomposition reactions , because the maximum surface atomic utilization as well as the controllably tailored physical and chemical properties. Amal et al reported employing Cu single atom catalysts (SACs) for electrochemical urea synthesis (Figure a–i) .…”