Synergy of Ru single atoms and nanoparticles on Br‐tethered covalent organic framework boosting reductive amination DOI

Qizhi Hu,

Ying Wen, Biao Meng

et al.

AIChE Journal, Journal Year: 2025, Volume and Issue: unknown

Published: May 20, 2025

Abstract Maximizing the atom efficiency of noble metal species is crucial for their application, but directly reducing size down to single atoms (SAs) limited when facing complex situations requiring simultaneous adsorption and activation multiple reactants. Herein, Schiff base condensation 1,3,5‐tris(4‐aminophenyl)benzene 2,5‐dibromoterephthalaldehyde offered a Br‐tethered covalent organic framework (COF) TAPB‐DBDH co‐loading ruthenium (Ru) SAs nanoparticles (NPs). We demonstrated triadic synergism Ru (Ru–C 3 N 1 ), NPs, in reductive aminations carbonyl compounds with ammonia hydrogen primary amines, showing high yield, large turnover number, frequency, stable recycling, broad substrate compatibility. A systematic theoretic experimental study revealed that cooperation provided strong affinity toward compound imine intermediate promote conversion, while co‐existed NPs lowered energy barrier H 2 cleavage.

Language: Английский

Multivariate covalent organic frameworks with tailored electrostatic potential promote nitrate electroreduction to ammonia in acid DOI Creative Commons

Qiyang Cheng,

Sisi Liu, Yanzheng He

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 19, 2025

The direct synthesis of ammonia from nitrate (NO3-) reduction in acid is a promising approach for industrialization. However, the difficulty arises intense competition with inevitable hydrogen evolution reaction, which favoured due to overwhelming protons (H+). Here, we systematically explore and rationally optimize microenvironment using multivariate covalent organic frameworks (COFs) as catalyst adlayers promote nitrate-to-ammonia conversion acid. With application tailored positive electrostatic potential generated over COFs, both mass transfer NO3- H+ are regulated via appropriate interactions, thus realizing priority NO3RR respect HER or NO3--to-NO2-. As result, an NH3 yield rate 11.01 mmol h-1 mg-1 corresponding Faradaic efficiency 91.0% attained, solid NH4Cl high purity 96.2% directly collected acid; therefore, this method provides practical economically valorising wastewater into valuable ammonia.

Language: Английский

Citations

0
Photochemically Stable Amide-Linked Covalent Organic Framework for Efficient Dual Photoredox and Copper Catalysis DOI

Zhi‐Bei Zhou,

Yingjie Fan,

Abigail L. Blenko

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8724 - 8732

Published: May 8, 2025

Language: Английский

Citations

0
Neighboring Effect of Adjacent Nitrogen Sites on Vinylene Linkage in Covalent Organic Frameworks for Regulating Oxygen Reduction Reaction DOI
Zhiqiang Zhu,

Huayun Ma,

Xiangtao Kong

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: May 12, 2025

Vinylene-linked covalent organic frameworks (COFs) are attractive electrocatalysts owing to their corresponding high chemical stability and excellent conjugated frameworks. In this study, for the first time, methyl group of pyrimidine ring was used synthesize COFs (TB-TFT-COF TB-TFC-COF) with vinylene linkages, which were employed as catalysts oxygen reduction reaction (ORR). addition, local electronic structures linkages could be regulated by adjacent nitrogen atomic sites various functional moieties (triazine, pyridine, pyrimidine), resulting in tunable electrocatalytic activity selectivity COFs. Notably, TB-TFT-COF attained a half-wave potential 0.74 V relative RHE alongside superior electrochemical stability, matching performance metal-free COF-based ORR. Furthermore, evidenced density theory (DFT) calculations, unit around linkage crucial enhancing utilization active sites. This work establishes that precise modulation coupling between neighboring enables development efficient catalysts.

Language: Английский

Citations

0
Cu atom pairs within covalent organic frameworks facilitate the photocatalytic reduction of CO2 to C2H6 DOI
Xinying Chen, Chunyu Liu, Tingyu Yang

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2025, Volume and Issue: unknown, P. 125499 - 125499

Published: May 1, 2025

Language: Английский

Citations

0
Synergy of Ru single atoms and nanoparticles on Br‐tethered covalent organic framework boosting reductive amination DOI

Qizhi Hu,

Ying Wen, Biao Meng

et al.

AIChE Journal, Journal Year: 2025, Volume and Issue: unknown

Published: May 20, 2025

Abstract Maximizing the atom efficiency of noble metal species is crucial for their application, but directly reducing size down to single atoms (SAs) limited when facing complex situations requiring simultaneous adsorption and activation multiple reactants. Herein, Schiff base condensation 1,3,5‐tris(4‐aminophenyl)benzene 2,5‐dibromoterephthalaldehyde offered a Br‐tethered covalent organic framework (COF) TAPB‐DBDH co‐loading ruthenium (Ru) SAs nanoparticles (NPs). We demonstrated triadic synergism Ru (Ru–C 3 N 1 ), NPs, in reductive aminations carbonyl compounds with ammonia hydrogen primary amines, showing high yield, large turnover number, frequency, stable recycling, broad substrate compatibility. A systematic theoretic experimental study revealed that cooperation provided strong affinity toward compound imine intermediate promote conversion, while co‐existed NPs lowered energy barrier H 2 cleavage.

Language: Английский

Citations

0