Main‐Group Metal Single‐Atomic Regulators in Dual‐Metal Catalysts for Enhanced Electrochemical CO₂ Reduction

Abstract

Single‐atom sites can not only act as active centers, but also serve as promising catalyst regulators and/or promoters. However, in many complex reaction systems such as electrochemical CO2 reduction reaction (CO2RR), the introduction of single‐atom regulators may inevitably induce the competitive hydrogen evolution reaction (HER) and thus reduce the selectivity. Here, the authors demonstrate that introducing HER‐inert main‐group metal single atoms adjacent to transition‐metal single atoms can modify their electronic structure to enhance the CO2RR to CO without inducing the HER side reaction. Dual‐metal Cu and In single‐site atoms anchored on mesoporous nitrogen‐doped carbon (denoted as Cu‐In‐NC) are prepared by the pyrolysis of a multimetallic metal–organic framework. Cu‐In‐NC shows a high faradic efficiency of 96% toward CO formation at −0.7 V versus reversible hydrogen electrode, superior to that of its monometallic single‐atom counterparts. Density functional theory studies reveal that the HER‐inert In sites can activate the adjacent Cu sites through electronic modifications, strengthening the binding of *COOH intermediate and thus boosting the electrochemical reduction of CO2 to CO.

Hierarchically ordered porous carbon with atomically dispersed cobalt for oxidative esterification of furfural

“…[18][19][20][21][22][23][24][25][26][27][28] In particular, N-rich zeolitic imidazolate frameworks (ZIFs) have been utilized as ideal precursors for the fabrication of SACs with catalytically active MN x centers. [29][30][31][32][33][34][35][36][37] However, the microporous nature of most ZIFs results in derived SACs with low porosity, which would greatly hinder the mass transfer of reactants and the accessibility of active sites. Recently, we reported a three-dimensional (3D) ordered macroporous ZIF-8 single crystal (SOM-ZIF-8), 38 which can serve as an ideal template/precursor for the construction of SACs with a 3Dordered macroporous (3DOM) structure.…”

A high-efficiency zirconium-based single-atom catalyst for the transformation of biomass-derived 5 hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan with nearly 100% selectivity

“…The high-resolution spectra of N 1s could be deconvoluted into five peaks at 398.7 eV, 399.8 eV, 400.7 eV, 401.9 eV and 403.8 eV (Fig. 3C), which were attributed to pyridinic-N, Zr–N, pyrrolic-N, graphitic-N and oxidized-N, 84 respectively. Compared with NC (Fig.…”

Multi-atom cluster catalysts for efficient electrocatalysis

“…3b). 79–86 As such, Jiang et al established TM 2 @C 2 N (M = Pt, Co, Ni, Cu) dual atom models and compared them with their counterpart TM@C 2 N for ORR. 87 Taking Co 2 @C 2 N as an example, Co 2 @C 2 N presented remarkably higher adsorption energy (2.39 eV) for the O 2 molecule with side-on binding configuration than Co@C 2 N (1.18 eV) with end-on binding configuration.…”