Proton capture strategy for enhancing electrochemical CO2 reduction on atomically dispersed metal-nitrogen active sites

Abstract

Electrocatalysts play a key role in accelerating the sluggish electrochemical CO2 reduction (ECR) involving multi-electron and proton transfer. Herein, we develop a proton capture strategy via accelerating the water dissociation reaction catalyzed by transition metal nanoparticles (NPs) adjacent to atomically dispersed Ni-Nx active sites (Ni@NiNCM) to accelerate the proton transfer to the latter for boosting the intermediate protonation step, and hence the whole ECR process. For the first time, the accelerated protonation process is amply demonstrated experimentally. Aberration-corrected scanning transmission electron microscopy and synchrotron radiation X-ray absorption spectroscopy, together with DFT calculations, revealed that the Ni NPs accelerated the adsorbed H (Had) generation and transfer to the adjacent Ni-Nx sites for boosting the intermediate protonation and the overall ECR processes. This proton capture strategy is highly general, which can be extended to the design and preparation of various high-performance catalysts for diverse electrochemical reactions even beyond ECR.

Nurturing the marriages of single atoms with atomic clusters and nanoparticles for better heterogeneous electrocatalysis

“…Reproduced with permission. [100] Copyright 2021, John Wiley and Sons ORR (E 1/2 = 0.870 V) and OER (η 10 = 380 mV) in alkaline media. [118] 5.5.2 | Electrocatalysis involving H 2 HER is an important electrocatalytic reaction for green production of hydrogen.…”

“…All these indicate that the single‐atom decoration endows the ingenious modulation of charge states and catalytic activity of Ru nanoparticles. The anchoring style has also been extensively studied with the Ni/Ni‐N 4 , [ 100 ] Ru/Fe‐N x , [ 101 ] Ru/Ru‐N x . [ 102 ] It should be noted that the above cooperative effect of these anchoring‐type sites employed simplified theoretical models, which diminish the particle size into cluster model or even atomic aggregation.…”

“…Hou and co-workers utilized the Ni@NiNCM as an efficient synergistic catalyst for electrochemically catalyzing CO 2 into the CO product. [100,117] Compared with NiNCM with one-fold Ni-N x sites, the Ni@NiNCM with additional Ni active species could achieve a much higher current density towards CO 2 RR (Figure 12N). The product was dominant CO without any liquid product.…”

Electrocatalytic CO2 reduction towards industrial applications

“…Catalysts are of great importance for decreasing the reaction energy barrier and improving the reaction rate and energy efficiency. 100 In eCO 2 RR, CO 2 is first adsorbed to catalysts, which provide a single electron to form a highly active CO 102,103 In situ TEM can powerfully extract the structural features of nanoscale electrocatalysts, including size, shape, surface configuration, and crystal structure, even at the atomic level. 104 Mass spectrometry can enable monitoring of the reaction process during electrocatalysis, which is useful for the real-time qualitative analysis of eCO 2 RR products.…”

Nanocrystalline CoOxglass for highly-efficient alkaline hydrogen evolution reaction

“…7d), suggesting the enhanced hydrogen transfer kinetics for (10CeCrP)CoO x -NF-HER. 56,58 The C 4 -potential plots, lg(R 2 )-potential plots and KIE ratio values suggest that (10CeCrP)CoO x -NF-HER has high hydrogen amount, small hydrogen transfer resistance and fast hydrogen mobility on the surface.…”