Charge carrier dynamics investigation of Cu2S–In2S3 heterostructures for the conversion of dinitrogen to ammonia via photo-electrocatalytic reduction

Photoelectrochemical (PEC) N2 fixation in aqueous solutions under ambient conditions can produce ammonia and migration of hydrogen. However, the process is limited by photocathodes with poor conversion efficiency and low production rates. Therefore, the rational design of catalyst structures is required to improve the performance and photoelectric utilization efficiency. In addition, the micro-charge carrier concentration, lifetime, and mobility cannot be quantitatively analyzed. As a result, we cannot reasonably speculate on the interaction law of microscopic carriers and macroscopic properties. Here, we successfully developed a Cu2S–In2S3 heterostructure catalyst for an efficient photo-electrocatalytic nitrogen reduction reaction (PEC-NRR) possessing sufficient carriers to enable higher carrier mobility and a reasonable recombination lifetime in the PEC process. The micro parameters are first quantified through a self-established photo-charge extraction by linearly increasing voltage (photo-CELIV) device and used to analyze the relationship between micro parameters and macro performance; this is of great significance for the PEC-NRR. In addition, the rare earth fluoride BaGdF5: 30%Yb3+, 5%Er3+ (UCNP) material with an up-conversion effect was applied as an auxiliary light absorber to further broaden the range of sunlight absorption and reduce the ammonia reaction's energy consumption. These steps enable the Cu2S–In2S3 heterostructure catalyst to achieve a NH3 production rate of 23.6721 μg h−1 cm−2 and a higher faradaic efficiency (33.25% at −0.6 V versus the reversible hydrogen electrode) in aqueous solutions under ambient conditions. This special double-electrode structure provides new insights into the design of photoelectric catalytic electrodes.

• Publication year

  2021

• Venue

  Journal of Materials Chemistry

• Publication date

  2021-03-27

• Fields of study

  Materials Science, Chemistry, Engineering

• Identifiers
  DOI 10.1039/D1TA00581B
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar

• No claims are published for this paper.

• No concepts are published for this paper.

• Heterostructured Catalysts for Electrocatalytic and Photocatalytic Carbon Dioxide Reduction

  2020cited by this paper
• Photoelectrochemical Synthesis of Ammonia with Black Phosphorus

  2020cited by this paper
• K+ Ion Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons for Visible-Light Driven Photocatalytic Nitrogen Reduction.

  2019cited by this paper
• Interfacial Engineering of W2N/WC Heterostructures Derived from Solid‐State Synthesis: A Highly Efficient Trifunctional Electrocatalyst for ORR, OER, and HER

  2019cited by this paper
• Photoelectrochemical Synthesis of Ammonia on the Aerophilic-Hydrophilic Heterostructure with 37.8% Efficiency

  2019cited by this paper
• An Efficient Photoelectrochemical Route for the Ambient Reduction of N2 to NH3 based on Nanojunctions Assembled from MoS2 Nanosheets and TiO2.

  2019cited by this paper
• Interfacing Epitaxial Dinickel Phosphide to 2D Nickel Thiophosphate Nanosheets for Boosting Electrocatalytic Water Splitting.

  2019cited by this paper
• Facile Ammonia Synthesis from Electrocatalytic N2 Reduction under Ambient Conditions on N-Doped Porous Carbon

  2018cited by this paper
• Ambient Electrochemical Ammonia Synthesis with High Selectivity on Fe/Fe Oxide Catalyst

  2018cited by this paper
• Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst.

  2017cited by this paper
• Amorphizing of Au Nanoparticles by CeOx–RGO Hybrid Support towards Highly Efficient Electrocatalyst for N2 Reduction under Ambient Conditions

  2017cited by this paper
• Electro-synthesis of ammonia from nitrogen at ambient temperature and pressure in ionic liquids

  2017cited by this paper
• Tris(perfluortolyl)boran – eine Bor‐Lewis‐Supersäure

  2017cited by this paper
• Electrochemical Synthesis of NH3 at Low Temperature and Atmospheric Pressure Using a γ-Fe2O3 Catalyst

  2017cited by this paper
• Cesium lead halide perovskite quantum dot-based warm white light-emitting diodes with high color rendering index

  2017cited by this paper
• Robert Le Rossignol, 1884–1976: Engineer of the ‘Haber’ process

  2017cited by this paper
• Ambient nitrogen reduction cycle using a hybrid inorganic–biological system

  2017cited by this paper
• Photocatalytic Conversion of Nitrogen to Ammonia with Water on Surface Oxygen Vacancies of Titanium Dioxide.

  2017cited by this paper
• Nitrogen Photofixation over III-Nitride Nanowires Assisted by Ruthenium Clusters of Low Atomicity.

  2017cited by this paper
• Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes.

  2017cited by this paper
• Layered‐Double‐Hydroxide Nanosheets as Efficient Visible‐Light‐Driven Photocatalysts for Dinitrogen Fixation

  2017cited by this paper
• Ammonia Electrosynthesis with High Selectivity under Ambient Conditions via a Li+ Incorporation Strategy.

  2017cited by this paper
• Ammonia Synthesis from Nitrogen and Water by Electricity Using an Electrochemical Cell with Ru Catalyst, Hydrogen‐Permeable Pd‐Ag Membrane, and Phosphate‐Based Electrolyte

  2017cited by this paper
• Room-Temperature Electrocatalytic Synthesis of NH3 from H2O and N2 in a Gas–Liquid–Solid Three-Phase Reactor

  2017cited by this paper
• Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia

  2016cited by this paper
• Nanostructured photoelectrochemical solar cell for nitrogen reduction using plasmon-enhanced black silicon

  2016cited by this paper
• Electrocatalytic Nitrogen Fixation for Distributed Fertilizer Production

  2016cited by this paper
• Selective Dinitrogen Conversion to Ammonia Using Water and Visible Light through Plasmon-induced Charge Separation.

  2016cited by this paper
• Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage

  2015cited by this paper
• Complete nitrification by a single microorganism

  2015cited by this paper
• Electronic Supplementary Material ( ESI ) for Facet-Dependent Solar Ammonia Synthesis of BiOCl Nanosheets via a Proton-Assisted Electron Transfer Pathway

  2015cited by this paper
• Photochemical nitrogen conversion to ammonia in ambient conditions with FeMoS-chalcogels.

  2015cited by this paper
• Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets.

  2015cited by this paper
• Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3

  2014cited by this paper
• Synthesis and Characterization of CuxS (x = 1–2) Nanocrystals Formed by the Langmuir–Blodgett Technique

  2014cited by this paper
• Plasmon-induced ammonia synthesis through nitrogen photofixation with visible light irradiation.

  2014cited by this paper
• Challenges in reduction of dinitrogen by proton and electron transfer.

  2014cited by this paper
• Chemistry. New recipe produces ammonia from air, water, and sunlight.

  2014cited by this paper
• Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

  2013cited by this paper
• A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia.

  2011cited by this paper
• Nitrogen reduction: Molybdenum does it again.

  2011cited by this paper
• Nitrogen cycle electrocatalysis.

  2009cited by this paper
• Synthesis and shape-tailoring of copper sulfide/indium sulfide-based nanocrystals.

  2008cited by this paper
• Energy efficiency improvements in ammonia production—perspectives and uncertainties

  2005cited by this paper
• Time-dependent mobility and recombination of the photoinduced charge carriers in conjugated polymer/fullerene bulk heterojunction solar cells

  2005cited by this paper
• Mobility and density relaxation of photogenerated charge carriers in organic materials

  2004cited by this paper
• Hole drift mobility in μc-Si:H

  2001cited by this paper
• New method of drift mobility evaluation in μc-Si:H, basic idea and comparison with time-of-flight

  2000cited by this paper
• Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.

  1996cited by this paper
• Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set

  1996cited by this paper
• Mechanism of Molybdenum Nitrogenase.

  1996cited by this paper
• Generalized Gradient Approximation Made Simple.

  1996cited by this paper
• Far Infrared and Raman Optical Study of α- and β-In2S3 Compounds

  1981cited by this paper
• SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS

  1976cited by this paper

• Recent advances in photoelectrochemical ammonia synthesis

  2025cites this paper
• Ternary-heterojunction In2S3/Bi2S3/BiOBr catalyst with interfacial effect to enhance the photocatalytic degradation of organic dyes

  2025cites this paper
• Optimizing construction of fern-like Co3O4@Ni3Fe-LDH p-n heterojunction for boosting photo-assisted-electronic N2 reduction into NH3 and DFT calculation

  2024cites this paper
• Photoelectrocatalytic ammonia synthesis through a Bi2MoO6@CuO/CF composite photocatalyst

  2024cites this paper
• Enhanced Photocatalytic CO2 Reduction to CH4 via Phosphorus-doped Carbon Nitride with Cu-Cu Coordinated Sites

  2024cites this paper
• Emerging metal oxide/nitride protection layers for enhanced stability of silicon photoelectrodes in photoelectrochemical catalysis: Recent advancements and challenges

  2023cites this paper
• Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’

  2023cites this paper
• Loading PVDF polymer on BiFeO3 films as photoelectrodes for efficient piezoelectric-photoelectrochemical water splitting

  2023cites this paper
• 1D/2D heterojunctions of SnS2@MoO3 as an efficient and robust catalyst for boosting the visible photoelectric nitrogen fixation ability

  2023cites this paper
• Photocatalytic Ammonia Synthesis from Nitrate Reduction on Nickel Single-Atom Decorated on Defective Tungsten Oxide

  2023cites this paper
• Three-phase interface of SnO2 nanoparticles loaded on hydrophobic MoS2 enhance photoelectrochemical N2 reduction

  2022cites this paper