Modulating Hydrogen Exchange Capabilities by Heterogenizing Pd Nanoclusters onto Ni 3 C Multipods for Efficiently Driving the “Formaldehyde-Nitrate” Tandem Electrochemical System

作者：Zulakha Zafar, Bin Zhao, Rida Javed, Arunpandiyan Surulinathan, Xin Long, Muhammad Bilal Hussain, Ning Chen, Renfei Feng, Yu Zhang, Xian‐Zhu Fu, Jing‐Li Luo · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c11608 · 被引用次数：23 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Catalytic Processes in Materials Science、Advanced Photocatalysis Techniques

Nitrate and formaldehyde, common industrial byproducts and waterborne pollutants, pose serious environmental and health hazards, yet their efficient conversion remains challenging due to sluggish hydrogen (H*) transfer and limited recycling strategies. While recent studies have explored nitrate reduction (NO 3 RR) and formaldehyde oxidation (FOR) coupling, they faced critical limitations such as no H 2 generation, a lack of electricity output, and reliance on Cu-based catalysts prone to deactivation. This work presents Pd nanoclusters on nickel carbide (Pd nc -Ni 3 C) that serve as a noncopper bifunctional catalyst that possesses superior H* exchange capabilities enabling dual-directional catalysis of NO 3 RR and FOR. At the cathode, Pd nc -Ni 3 C achieves an onset potential of +0.27 V vs RHE, and 98% Faradaic efficiency for NH 3 at −0.3 V. At the anode, Pd nc -Ni 3 C achieves an efficient FOR at a low onset potential of 0.04 V and enables a broad oxidation window (0–1.2 V) with high current density (up to 910 mA cm –2 ), outperforming previously reported Cu- and Ni-based systems. Differential electrochemical mass spectra reveal a previously unexplored intermolecular coupling pathway for H 2 evolution, advancing mechanistic insight into the 1-electron formaldehyde oxidation process. By coupling the NO 3 RR and FOR, a high-performance “Formaldehyde–Nitrate” galvanic cell is achieved with an OCV of 0.88 V and peak power density of 7.4 mW cm –2 . Distinctively, this Ni based sys...