卟啉
尿素
化学
硝酸盐
电催化剂
光化学
电化学
组合化学
无机化学
有机化学
电极
物理化学
作者
Yi Tan,Xiaokang Chen,J. Yuan,Guan Sheng,Wei Deng,Hao Wu
标识
DOI:10.1002/ange.202513441
摘要
Traditional urea synthesis via the Bosch‐Meiser process suffers from high energy consumption and greenhouse gas emissions. Electrocatalytic urea production from CO2 and nitrate (NO3‐) under ambient conditions offers a sustainable alternative, yet challenges persist due to variable NO3‐ concentrations and competing side reactions. Herein, we propose porphyrin metal‐organic framework (PMOF) and Cu‐porphyrin MOF (Cu‐PMOF) catalysts for NO3‐ concentration‐adaptive urea synthesis. Density functional theory (DFT) calculations reveal that PMOF weakly adsorbs *NO2 via hydrogen bonding, favoring its coupling with *CO2, while Cu‐PMOF strongly binds *NO2 at Cu sites, facilitating spontaneous *NO/*CO coupling to form *OCNO intermediates under dilute NO3‐ conditions. Experimentally, PMOF achieves a urea yield of 28.6 μmol h‐1 mgcat‐1 and a Faradaic efficiency (FE) of 23.1% in 0.1 M NO3‐, whereas Cu‐PMOF outperforms in 0.05 M NO3‐ with a yield of 25.5 μmol h‐1 mgcat‐1 and FE of 52.7%. In situ spectroscopy and mechanistic study confirm distinct pathways: PMOF relies on stepwise coupling of *HNO2 with *CO2, while Cu‐PMOF enables consecutive *NO‐*CO coupling. This work highlights adaptive electrocatalyst design for efficient C‐N coupling, advancing sustainable urea synthesis.
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