Atomically Precise Dinuclear Site Active toward Electrocatalytic CO₂ Reduction

Abstract

The development of atomically precise dinuclear heterogeneous catalysts is promising to achieve efficient catalytic performance and is also helpful to the atomic-level understanding on the synergy mechanism under reaction conditions. Here, we report a Ni 2 (dppm) 2 Cl 3 dinuclear-cluster-derived strategy to a uniform atomically precise Ni 2 site, consisting of two Ni 1 −N 4 moieties shared with two nitrogen atoms, anchored on a N-doped carbon. By using operando synchrotron X-ray absorption spectroscopy, we identify the dynamically catalytic dinuclear Ni 2 structure under electrochemical CO 2 reduction reaction, revealing an oxygen-bridge adsorption on the Ni 2 −N 6 site to form an O−Ni 2 −N 6 structure with enhanced Ni−Ni interaction. Theoretical simulations demonstrate that the key O−Ni 2 −N 6 structure can significantly lower the energy barrier for CO 2 activation. As a result, the dinuclear Ni 2 catalyst exhibits >94% Faradaic efficiency for efficient carbon monoxide production. This work provides bottom-up target synthesis approaches and evidences the identity of dinuclear sites active toward catalytic reactions.

Activation of H2O tailored by interfacial electronic states at nanoscale interface for enhanced electrocatalytic hydrogen evolution

“…The concept of SWS dominated surface transient states to tune the concerted electron and proton enables optimization of the entire electrochemical interface as opposed to only catalysts structure to improve activity for the hydrogen evolution reaction, which is critical to designing more active electrochemical interfaces for energy storage and conversion reactions. This unique reaction mechanism may not only provide an important guidance for the design/selection of catalysts/electrolytes for the nanomaterial-catalyzed reactions in an aqueous environment, including CO 2 /CO reduction [85][86][87][88][89] , nitrogen reduction 17,90,91 , and other electrocatalytic reduction reactions 92 , but also shed new light on the nanoscale-range electron and proton transfer through the water-line 'bridge' in the biological macromolecule system [93][94][95] , which could follow the out sphere electron transfer model of Marcus theory with connected SWs as a bridge [96][97][98] . Author Contributions PYW and JFZ performed the main experiments and equally contribute to this research.…”

Dual‐Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications

“…A separate Ni 2 /N/C catalyst has also been tested in a flow cell configuration for CO 2 reduction, enabling higher CO current density. [194] Meanwhile, precious metal-based in-plane adjacent Ag 2 /N/C DACs for CO 2 reduction have been created by Li et al (Section 3.1.2). [195] Promisingly, TOF values for CO production were ∼6 times greater for the Ag DAC compared to separately synthesized Ag/N/C SAC (Figure 11c).…”

Low‐dimensional material supported single‐atom catalysts for electrochemical CO2 reduction

“…Yellow and cyan contours stand for electron accumulation and deletion, respectively. Reproduced with permission 147 . Copyright 2021, American Chemical Society.…”

“…A dynamic bridgeoxygen adsorption to form an O-Ni 2 -N 6 site was found to be the actual active site, effectively lowering the energy barrier of the activation of CO 2 to COOH* (Figure 8E,F). 147 Very recently, a catalyst with binuclear nickel bridging with nitrogen and carbon atoms (N 2 -N 4 -C 2 ) was also demonstrated to be better than that of Ni SAC. 150 In addition to homonuclear DMS catalysts mentioned above, the fabrication of heteronuclear DMS catalysts is also conductive to enhance the ECR performance.…”