Boosting photocatalytic nitrogen reduction reaction by Jahn-Teller effect.

J Colloid Interface Sci

Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology (CICAEET), Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), Joint International Research Laboratory of Climate and Environment Change (ILCEC), Jiangsu Engineering and Technology Research Center of Environmental Cleaning Materials (ECM), School of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu Road, Nanjing 210044, China; Donghai Laboratory, Zhoushan 316021, China. Electronic address:

Published: November 2023

AI Article Synopsis

  • Photocatalytic ammonia production is gaining attention over the traditional Haber-Bosch process due to its lower energy use and sustainable nature.
  • The study focuses on how MoO·0.55HO exhibits improved nitrogen reduction reactions compared to α-MoO, thanks to its structural differences that create more active sites for nitrogen adsorption.
  • MoO·0.55HO achieved an ammonia production rate of 88.6 μmol·g under visible light, outperforming α-MoO by 4.6 times, highlighting its potential for efficient photocatalytic applications.

Article Abstract

Compared with traditional the Haber-Bosch process, photocatalytic ammonia production has attracted a considerable attention due to its advantages of low energy consumption and sustainability. In this work, we mainly study the photocatalytic nitrogen reduction reaction (NRR) on MoO·0.55HO and α-MoO. Structure analysis shows that compared to α-MoO, the [MoO] octahedrons in MoO·0.55HO obviously distort (Jahn-Teller distortion), leading to the formation of Lewis acid active sites that favors the adsorption and activation of N. X-ray photoelectron spectroscopy (XPS) further confirms the formation of more Mo as Lewis acid active sites in MoO·0.55HO. Transient photocurrent, photoluminescence and electrochemical impedance spectra (EIS) confirmed that MoO·0.55HO has a higher charge separation and transfer efficiency than α-MoO. Density functional theory (DFT) calculation further confirmed that the N adsorption on MoO·0.55HO is more favorable thermodynamically than that on α-MoO. As a result, under visible light irradiation (λ ≥ 400 nm) for 60 min, an ammonia production rate of 88.6 μmol·g was achieved on MoO·0.55HO, which is about 4.6 times higher than that on α-MoO. In comparison to other photocatalysts, MoO·0.55HO exhibits an excellent photocatalytic NRR activity under visible light irradiation without using sacrificial agent. This work offers a new fundamental understanding to photocatalytic NRR from the viewpoint of crystal fine structure, which benefits designing efficient photocatalysts.

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.jcis.2023.06.191DOI Listing

Publication Analysis

Top Keywords

photocatalytic nitrogen
8
nitrogen reduction
8
reduction reaction
8
ammonia production
8
formation lewis
8
lewis acid
8
acid active
8
active sites
8
visible light
8
light irradiation
8

Similar Publications

Conjugated polymers, represented by polymeric carbon nitrides (PCNs), have risen to prominence as new-generation photocatalysts for overall water splitting (OWS). Despite considerable efforts, achieving highly crystalline PCNs with minimal structural defects remains a great challenge, and it is also difficult to examine the exact impact of complex defect states on OWS process, which largely limits their quantum efficiency. Herein, we devise a 'in-situ salt flux' assisted copolymerization protocol by using nitrogen-rich and nitrogen-deficient monomers to precisely manipulate the structural defects of poly (triazine imide) (PTI) single crystals.

View Article and Find Full Text PDF

Carbon dots (CDs) mediated g-CN (CN) is a promising visible-light-driven semiconductor in catalyzing peroxymonosulfate (PMS) for aqueous contaminants remediation. However, the poor dispersibility of powered catalyst and its challenging recyclability impede their broader application. Herein, we embedded FeN bridge within the g-CN framework and immobilized g-CN gel beads (CA/FNCCN) through a 3D cross-linking process with sodium alginate.

View Article and Find Full Text PDF

Solar-driven CO2 reduction to ethanol is extremely challenging due to the limited efficiency of charge separation, sluggish kinetics of C-C coupling, and unfavorable formation of oxygenate intermediates. Here, we elaborately design a red polymer carbon nitride (RPCN) consisting of S-N and Cu-N4 dual active sites (Cu/S-RPCN) to address this challenge, which achieves an impressive ethanol evolution rate of 50.4 µmol g-1 h-1 with 99.

View Article and Find Full Text PDF

Leveraging an Innovative Green Copper and Nitrogen-Doped Carbon Quantum Dots for Quantification of Malathion in Various Matrices.

J Fluoresc

January 2025

Pharmaceutical Analytical Chemistry Department, Faculty of Pharmacy, Al-Azhar University, Assiut branch, Assiut, 71524, Egypt.

Article Synopsis
  • Carbon quantum dots (CQDs) are gaining attention as cost-effective and eco-friendly fluorescence probes, offering advantages over traditional luminescent techniques.
  • A new type of copper and nitrogen-doped CQDs (Cu-N@CQDs) was created, achieving a high quantum yield of 40.20% for detecting malathion, an insecticide.
  • The study demonstrated that the fluorescence intensity of Cu-N@CQDs decreased in response to malathion, allowing for accurate measurements across various samples like water and food, achieving high recovery rates.
View Article and Find Full Text PDF

BrCFCN for photocatalytic cyanodifluoromethylation.

Nat Commun

January 2025

Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 200032, Shanghai, China.

Considering the unique electronic properties of the CF and the CN groups, the CFCN group has significant potential in drug and agrochemical development, as well as material sciences. However, incorporating a CFCN group remains a considerable challenge. In this work, we disclose a use of bromodifluoroacetonitrile (BrCFCN), a cost-effective and readily available reagent, as a radical source for cyanodifluoromethylation of alkyl alkenes, aryl alkenes, alkynes, and (hetero)arenes under photocatalytic conditions.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!