Urea Electrosynthesis from Nitrate and CO₂ on Diatomic Alloys

2024/06/14 by Kai Chen, Danyang Ma, Ying Zhang +7
Chemical Engineering · Energy · #Advanced Photocatalysis Techniques #Ammonia Synthesis and Nitrogen Reduction #CO2 Reduction Techniques and Catalysts

paper · pdf · doi:10.1002/adma.202402160

openalex publication_date 2024/06/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

Abstract Urea electrosynthesis from co–electrolysis of NO 3 − and CO 2 (UENC) offers a promising technology for achieving sustainable and efficient urea production. Herein, a diatomic alloy catalyst (CuPd 1 Rh 1 –DAA), with mutually isolated Pd and Rh atoms alloyed on Cu substrate, is theoretically designed and experimentally confirmed to be a highly active and selective UENC catalyst. Combining theoretical computations and operando spectroscopic characterizations reveals the synergistic effect of Pd 1 –Cu and Rh 1 –Cu active sites to promote the UENC via a tandem catalysis mechanism, where Pd 1 –Cu site triggers the early C–N coupling and promotes *CO 2 NO 2 –to–*CO 2 NH steps, while Rh 1 –Cu site facilitates the subsequent protonation step of *CO 2 NH 2 to *COOHNH 2 toward the urea formation. Impressively, CuPd 1 Rh 1 –DAA assembled in a flow cell presents the highest urea Faradaic efficiency of 72.1% and urea yield rate of 53.2 mmol h −1 g cat −1 at −0.5 V versus RHE, representing nearly the highest performance among all reported UENC catalysts.

Citations

• Structural Sensitivities in Bimetallic Catalysts for Electrochemical CO₂ Reduction Revealed by Ag–Cu Nanodimers
• Coupling N2 and CO2 in H2O to synthesize urea under ambient conditions
• Single-Atom Alloy Catalysis
• Unveiling Electrochemical Urea Synthesis by Co‐Activation of CO₂ and N₂ with Mott–Schottky Heterostructure Catalysts
• A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate
• Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst
• Selective electrocatalytic synthesis of urea with nitrate and carbon dioxide
• Highly selective electroreduction of N ₂ and CO ₂ to urea over artificial frustrated Lewis pairs
• Unveiling the Synergy of O‐Vacancy and Heterostructure over MoO_3‐<i>_x</i>/MXene for N₂ Electroreduction to NH₃
• A Defect Engineered Electrocatalyst that Promotes High-Efficiency Urea Synthesis under Ambient Conditions
• Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst
• Oxygen Vacancy-Mediated Selective C–N Coupling toward Electrocatalytic Urea Synthesis
• Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst
• Ambient Electrosynthesis of Urea with Nitrate and Carbon Dioxide over Iron‐Based Dual‐Sites
• Single‐Atom Bi Alloyed Pd Metallene for Nitrate Electroreduction to Ammonia
• Review on Electrocatalytic Coreduction of Carbon Dioxide and Nitrogenous Species for Urea Synthesis
• Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia
• Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites
• Selective electrochemical synthesis of urea from nitrate and CO2 via relay catalysis on hybrid catalysts

Related

• Recent Advances in Urea Electrocatalysis: Applications, Materials and Mechanisms †
• Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst
• Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites
• Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis
• Oxide-Derived Core–Shell Cu@Zn Nanowires for Urea Electrosynthesis from Carbon Dioxide and Nitrate in Water