Anchoring Ultrafine β‐Mo2C Clusters Inside Porous Co‐NC Using MOFs for Electric‐Powered Coproduction of Valuable Chemicals

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 20; no. 32; pp. e2401226 - n/a
• Main Authors: Chen, Yu‐Zhen, Fan, Yi‐Wen, Wang, Yang, Li, Zhibo
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01-08-2024
• Subjects: Aldehydes; Amines; Anodizing; Clusters; Density functional theory; Electrocatalysts; Fine chemicals; green chemicals electrosynthesis; heterojunction; Heterojunctions; Heterostructures; Metal-organic frameworks; metal–organic framework; molybdenum carbide cluster; Oxidation; Reaction kinetics; selective alcohols oxidation; Ultrafines
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202401226

Electroredox of organics provides a promising and green approach to producing value‐added chemicals. However, it remains a grand challenge to achieve high selectivity of desired products simultaneously at two electrodes, especially for non‐isoelectronic transfer reactions. Here a porous heterostructure of Mo2C@Co‐NC is successfully fabricated, where subnanometre β‐Mo2C clusters (<1 nm, ≈10 wt%) are confined inside porous Co, N‐doped carbon using metalorganic frameworks. It is found that Co species not only promote the formation of β‐Mo2C but also can prevent it from oxidation by constructing the heterojunctions. As noted, the heterostructure achieves >96% yield and 92% Faradaic efficiency (FE) for aldehydes in anodic alcohol oxidation, as well as >99.9% yield and 96% FE for amines in cathodal nitrocompounds reduction in 1.0 M KOH. Precise control of the reaction kinetics of two half‐reactions by the electronic interaction between β‐Mo2C and Co is a crucial adjective. Density functional theory (DFT) gives in‐depth mechanistic insight into the high aldehyde selectivity. The work guides authors to reveal the electrooxidation nature of Mo2C at a subnanometer level. It is anticipated that the strategy will provide new insights into the design of highly effective bifunctional electrocatalysts for the coproduction of more complex fine chemicals.
A porous heterostructure of Mo2C@Co‐NC is successfully fabricated with a high loading of surface Mo2C species templated by MOFs. The porous Co‐NC can effectively prompt the formation of β‐Mo2C to fabricate the heterojunction and keep the adjacent β‐Mo2C from deactivation. The heterostructure achieves high yield and Faradaic efficiency of desired products from two non‐isoelectronic transfer reactions at two electrodes.