Enhancing CO2 Electroreduction to C2 Products on Metal-Nitrogen Sites by Regulating H2O Dissociation.

Water dissociation remarkably affects the CO2 reduction to CO and HCOOH, but whether it is effective for two-carbon product formation on M-Nx-containing catalysts is still ambiguous. Herein, by using a fluorinated metal phthalocyanine (MPc-F) as the M-N4-based model electrocatalyst, experimental and theoretical results reveal that the H2O-dissociation-induced active H species decrease the overpotential of the *CO hydrogenation to *CHO and facilitate the C-C coupling between *CHO and neighboring CO. Such an effect is strengthened by an increase in the *CO binding strength on the metal center. By introducing CuPc as the H2O dissociation catalyst into MPc-F (MPc-F/CuPc) to accurately regulate the H2O dissociation, the faradic efficiency of C2 products on FePc-F/CuPc and MnPc-F/CuPc increases from 0% (FePc-F and MnPc-F) to 26 and 36%, respectively. This work develops a novel strategy for enhancing the selectivity of M-Nx-containing catalysts to C2 products and reveals the correlation between H2O dissociation and C2 product formation.

Two-dimensional metal-organic frameworks and their derivatives for electrochemical energy storage and electrocatalysis.

Two-dimensional (2D) metal-organic frameworks (MOFs) and their derivatives with excellent dimension-related properties, e.g. high surface areas, abundantly accessible metal nodes, and tailorable structures, have attracted intensive attention as energy storage materials and electrocatalysts. A major challenge on the road toward the commercialization of 2D MOFs and their derivatives is to achieve the facile and controllable synthesis of 2D MOFs with high quality and at low cost. Significant developments have been made in the synthesis and applications of 2D MOFs and their derivatives in recent years. In this review, we first discuss the state-of-the-art synthetic strategies (including both top-down and bottom-up approaches) for 2D MOFs. Subsequently, we review the most recent application progress of 2D MOFs and their derivatives in the fields of electrochemical energy storage (e.g., batteries and supercapacitors) and electrocatalysis (of classical reactions such as the HER, OER, ORR, and CO2RR). Finally, the challenges and promising strategies for the synthesis and applications of 2D MOFs and their derivatives are addressed for future development.

Ultrasmall 2 D Cox Zn2-x (Benzimidazole)4 Metal-Organic Framework Nanosheets and their Derived Co Nanodots@Co,N-Codoped Graphene for Efficient Oxygen Reduction Reaction.

The development of nonprecious metal-nitrogen-carbon (M-N-C) materials with efficient metal utilization and abundant active sites for the oxygen reduction reaction (ORR) is of great significance for fuel cells and metal-air batteries. Ultrasmall 2 D Cox Zn2-x (benzimidazole)4 [Cox Zn2-x (bim)4 ] bimetallic metal-organic framework (MOF) nanosheets (≈2 nm thick) are synthesized by a novel bottom-up strategy and then thermally converted into a core-shell structure of sub-5 nm Co nanodots (NDs) wrapped with 2 to 5 layers of Co,N-codoped graphene (Co@FLG). The size of the Co NDs in Co@FLG could be precisely controlled by the Co/Zn ratio in the Cox Zn2-x (bim)4 nanosheet. As an ORR electrocatalyst, the optimized Co@FLG exhibits an excellent half-wave potential of 0.841 V (vs. RHE), a high limiting current density of 6.42 mA cm-2 , and great stability in alkaline electrolyte. Co@FLG also has great ORR performance in neutral electrolyte, as well as in Mg-air batteries. The experimental studies and DFT calculations reveal that the high performance of Co@FLG is mainly attributed to its great O2 absorptivity, which is endowed by the abundant Co-Nx and pyridinic-N in the FLG shell and the strong electron-donating ability from the Co ND core to the FLG shell. This elevates the eg orbital energy of CoII and lowers the activation energy for breaking the O=O/O-O bonds. This work sheds light on the design and fabrication of 2 D MOFs and MOF-derived M-N-C materials for energy storage and conversion applications.