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A Combined Experimental and Theoretical Insights into the Synergistic Effect of Cerium Doping and Oxygen Vacancies into BaZrO <sub/>3-δ</sub> Hollow Nanospheres for Efficient Photocatalytic Hydrogen Production
摘要： The long-standing debate over the influence of oxygen vacancies and various dopants has been the center point in perovskite-based compounds for their photocatalytic applications. Hydrothermally synthesized Cerium doped BaZrO3 (BZO) hollow nanospheres has been systematically studied by experimental and theoretical calculations to understand the effect of Cerium doping and oxygen vacancies on the photocatalytic properties. Compounds synthesized by a template-free route were composed of hollow nanospheres generated by Ostwald ripening of spherical nanospheres, which were formed by agglomeration of nanoparticles. The high alkaline condition and high temperature during the hydrothermal condition may lead to the formation of local disorders and oxygen vacancies in the compounds, confirmed by ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) analysis and density functional theoretical (DFT) calculations. Combination of oxygen vacancies and progressive doping of Ce onto BZO, BaZr1–xCexO3 (x = 0.00 – 0.04), creates additional energy levels stipulated by vacancy defects and Ce mixed valance states within the band gap of BZO thereby reducing its band gap. The photocatalytic efficacy of the compounds has been examined by photo-driven H2 generation concomitant with oxidation of a sacrificial donor. In this study, BaZr0.97Ce0.03O3 shows the highest efficiency (823 μmol h-1 g-1) with an apparent quantum yield (AQY) of 6% in photocatalytic H2 production among all five synthesized samples. The data obtained from the UV–Vis DRS, XPS, ESR analysis and DFT calculations, the synergistic effect of decreasing the band gap due to Ce doping and the presence of Ce (III)/Ce (IV) pairs along with oxygen vacancies and lattice distortions could be the reasons behind the enhanced photocatalytic efficacy of BaZr1–xCexO3 (x = 0.00 – 0.04) under UV–Visible light.
关键词： Photocatalytic hydrogen production,Cerium doping,Oxygen vacancies,BaZrO3,Hollow nanospheres
更新于2025-11-21 11:01:37
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Photocatalytic Reforming of Sugar and Glucose into H2 over Functionalized Graphene Dots
摘要： Photocatalytic reforming of biomass into H2 combining with its photosynthesis counterpart constitutes a sustainable carbon cycle that produces a clean solar fuel. This study reports the use of environmentally benign graphene-based photocatalysts to effectively reform sugar and glucose. We produce a catalyst consisting of sulfur and nitrogen codoped graphene oxide dots (SNGODs) by sequentially annealing graphite-derived graphene oxide with sulfur and ammonia, exfoliating the annealed product into dots, and autoclaving the dots in an ammonia solution. The codoping introduces quaternary nitrogen on the graphene basal plane to patch the vacancy defects and the autoclaving creates a conjugation between the nitrogen nonbonding states and the graphitic-π orbital by introducing peripheral amide and amino groups. These functionalization steps enlarge the electron resonance domain, narrowing the bandgap and inducing charge delocalization and separation. Here, when SNGODs deposited with a Pt cocatalyst effectively catalyzed H2 production from aqueous solutions of sugar and glucose under visible light irradiation for more than 80 h. The apparent quantum yields of the reforming of sugar and glucose reach 11% and 7.4%, respectively, under 420-nm monochromatic irradiation. This pioneer study demonstrates the superiority of using carbon-based photocatalysts for biomass reforming and provides a structure-tuning strategy for enhancing the catalytic activity.
关键词： Reforming of sugar,Hydrogen production,Graphene oxide,Reforming of glucose,Photocatalytic reforming
更新于2025-11-20 15:33:11
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Synergistic effect of g-C3N4, Ni(OH)2 and halloysite in nanocomposite photocatalyst on efficient photocatalytic hydrogen generation
摘要： Here, we develop a strategy to improve the visible-light-driven photocatalytic hydrogen evolution activity of g-C3N4 by compositing it with low-cost Ni(OH)2 nanoplatelets and inexpensive and earth-abundant halloysite nanotubes. The Ni(OH)2@g-C3N4/halloysite nanocomposite photocatalyst with different amounts of Ni(OH)2 (0.5–10 wt%) were prepared, and a synergistic effect of Ni(OH)2 platelets and halloysite nanotubes on physicochemical properties and photocatalytic hydrogen evolution activity of g-C3N4 was investigated. As expected, the Ni(OH)2@g-C3N4/halloysite nanocomposite photocatalyst prepared with 1 wt% Ni(OH)2 exhibited the highest photocatalytic hydrogen evolution rate (18.42 μmol·h–1) which is much higher than that of g-C3N4 (0.43 μmol·h–1) and Ni(OH)2@g-C3N4 (9.12 μmol·h–1). Such enhancement in photocatalytic activity of Ni(OH)2@g-C3N4/halloysite nanocomposite photocatalyst is attributed to efficient transfer of photogenerated electrons from the g-C3N4 to Ni(OH)2 cocatalyst interface and trapping of photogenerated holes on the negatively charged surfaces of halloysite nanotubes. In addition, adsorption affinity of the water and methanol molecules was modeled using different surfaces of Ni(OH)2, halloysite-7?, and g-C3N4 and it is found that combining the g-C3N4 with halloysite-7? and Ni(OH)2 can significantly improve the adsorption of water and methanol molecules on the surface of the developed nanocomposite. This study offers a simple approach for developing an efficient and inexpensive nanocomposite for effective and applied photocatalytic water splitting methodology for hydrogen production and other possible optoelectronic and photocatalytic applications.
关键词： Halloysite,g-C3N4,Water splitting,Nanocomposite,Hydrogen production,Ni(OH)2
更新于2025-11-19 16:51:07
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Insights into the thermo-photo catalytic production of hydrogen from water on a low-cost NiOx-loaded TiO2 catalyst
摘要： Thermo-photo catalytic water splitting, where the introduction of thermal energy increases the oxidation driving force for narrow-band-gap photocatalysts (with a low valence band potential), exhibited significantly advanced performance for hydrogen production compared with general water splitting at room temperature. Herein, a low-cost NiOx-loaded TiO2 catalyst was reported for thermo-photo catalytic water splitting with methanol as the sacrificial agent. The catalyst with an optimal Ni ratio of 5 wt.% achieved a hydrogen evolution rate of 53.7 mmol/h/g under simulated AM 1.5G sunlight at 260℃, which was 2.5 times more than that without illumination, with apparent quantum efficiencies of 66.24%, 33.55%, 32.52% and 15.35% at 380, 420, 450 and 500 nm, respectively. More impressively, under the irradiation of visible light (λ>420 nm) at this temperature, and photohydrogen yield could still reach 26.9 mmol/h/g, which was 5 orders of magnitude greater than that (0.0011 mmol/h/g) conducted at room temperature. Isotope tracer experiments demonstrated that the introduction of photo energy promoted the hydrogen production mainly by enhancing hydrogen evolution from water splitting rather than methanol decomposition or reformation. Furthermore, the step-wise reaction mechanism was revealed with insights into the synergistic roles of thermo-energy and photo-energy for production of hydrogen from water. Those findings highlight the great promise of thermo-photo catalysis and should inspire more efforts for water splitting.
关键词： visible light,Hydrogen production,nickel-based catalysts,thermo-photo catalysis,titanium dioxide
更新于2025-11-14 17:03:37
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Hydrogen production via a novel two-step solar thermochemical cycle based on non-volatile GeO2
摘要： Encouraged by recent advances in solar-chemical fuel production, a moderately high-temperature solar thermochemical cycle based on GeO2/Ge is investigated thermodynamically. Since the GeO2/Ge redox has a great oxygen exchange capacity and suffers unfavorable phase change at high temperature, methanothermal reduction is introduced to lower the operation temperature below melting point of redox. The calculated results indicate that reduction conditions of 875 K < T_red < 1200 K and CH4:GeO2 = 2:1 are conducive to achieving high selectivities of H2 and CO. As for the oxidation step, the H2O:Ge ratio of 8:1 is found abundant enough to ensure complete reoxidation of Ge. Isothermal and non-isothermal solar-to-fuel efficiency (η_solarfuel) are compared, where η_solarfuel of 0.47 and isothermal η_solarfuel of 0.28 respectively. In addition, the preferred site of CH4 adsorbing on GeO2 is predicted, and the calculated adsorption energy is lower than that of SnO2, indicating that GeO2 could be a suitable material for substrate before methanothermal reduction.
关键词： Non-volatile redox,Isothermal and nonisothermal operation,Syngas production,Hydrogen production,GeO2/Ge based solar-chemical cycle
更新于2025-09-23 15:23:52
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Z-Scheme 2D/2D Heterojunction of Black Phosphorus/Monolayer Bi2WO6 Nanosheets with Enhanced Photocatalytic Activities
摘要： Black phosphorus (BP), a star-shaped two-dimensional material, has attracted considerable attention owing to its unique chemical and physical properties. BP shows great potential in photocatalysis area because of its excellent optical properties; however, its applications in this field have been limited to date. Herein, we design and fabricate a Z-Scheme heterojunction of 2D/2D BP/monolayer Bi2WO6 (MBWO) by a simple and effective method. The BP/MBWO heterojunction exhibits enhanced photocatalytic performance in photocatalytic water splitting to produce H2 and NO removal to purify air; the highest H2 evolution rate of BP/MBWO is 21042 μmol g-1, is 9.15 times that of pristine MBWO and the NO removal ratio was as high as 67%. A Z-Scheme photocatalytic mechanism is proposed based on monitoring of ?O2?, ?OH, NO2, and NO3? species in the reaction. This work broadens applications of BP and highlights its promise in the treatment of environmental pollution and renewable energy issues.
关键词： hydrogen production,photocatalytic,Black phosphorus,2D/2D heterojunction,Z-Scheme
更新于2025-09-23 15:23:52
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2D-montmorillonite-dispersed g-C3N4/TiO2 2D/0Dnanocomposite for enhanced photo-induced H2 evolution from glycerol-water mixture
摘要： Montmorillonite (MMT) dispersed g-C3N4/TiO2 hybrid nanocomposite for enhanced photo-catalytic hydrogen production from glycerol-water mixture has been investigated. The newly designed composite photo-catalysts were fabricated through a sol-gel assisted hydrothermal method and were characterized by XRD, XPS, SEM, EDX, TEM, FTIR, UV–Vis, Raman and PL spectroscopy. Well-designed g-C3N4/MMT/TiO2 heterojunction composite was obtained with 2D MMT structure, which promoted both visible light absorption and hindered charges recombination rate. The modification of 2D/0D g-C3N4/TiO2 heterojunction with 2D MMT sheets enhances H2 production due to MMT works as a mediator for effective charges trapping and transportation within the composite structure. The g-C3N4/MMT/TiO2 photo-catalyst exhibits highest H2 production of 4425 ppm h?1 g?1 at pH 7.0, which was 2.12 times higher than the pure TiO2 (2085 ppm h?1 g?1). In addition, increasing catalyst loading promotes more H2 evolution and among the different sacrificial reagents, glycerol-water mixture gave highest H2 production due to the presence of α-hydrogen atoms attached to carbon atoms. The enhanced photocatalytic efficiency can be attributed to synergistic effect of MMT with g-C3N4/TiO2 heterojunction composite, appropriate band structure and transportation of electrons–holes with their hindered recombination rate. These composite catalysts exhibited excellent photo-catalytic stability for H2 production in cyclic runs. Possible reaction mechanism for hydrogen production over g-C3N4/MMT/TiO2 composite has been explained based on the experimental results. The finding of this work would be fruitful for hydrogen production applications with all sustainable systems.
关键词： TiO2,Photo-catalysis,Montmorillonite,g-C3N4,Z-scheme,Hydrogen production
更新于2025-09-23 15:23:52
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A review on photoelectrochemical hydrogen production systems: Challenges and future directions
摘要： Water photolysis is a fundamental concept in which solar-driven water splitting is utilized to generate renewable hydrogen fuel using semiconductor-based electrochemical systems. The engineering design principles for each system configuration, including single, dual/tandem photoelectrodes, tandem photoelectrochemical-photovoltaic, and multi-junction designs are reviewed. Modeling and numerical simulation of photoelectrochemical processes based on up-to-date multi-scale analysis are presented and discussed. In addition, the achievements made in semiconductor photoelectrode materials and the rational engineering methods needed to improve the solar to hydrogen efficiency are demonstrated. Furthermore, some key accomplishments in different aspects, such as electron-hole recombination, stability, photocorrosion, energy band gap, and photocurrent density are discussed. Moreover, key points on the challenges, opportunities and future directions towards commercialization of viable photoelectrochemical reactors are discussed.
关键词： Semiconductor materials,Photoelectrochemical process,Hydrogen production,Solar energy
更新于2025-09-23 15:23:52
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Optimizing one-dimensional TiO2 for photocatalytic hydrogen production from a water-ethanol mixture and other electron donors
摘要： This work is focused on synthesizing and employing one-dimensional (1D) titanium dioxide (TiO2) for hydrogen (H2) production. Based on using electron donors (EDs) (ethanol, methanol, formic acid and 1,2,3 propanetriol), the increased H2 production, when compared to P25 TiO2 nanoparticles, was due to the large specific surface area (SSA) and enhanced electron mobility of 1D TiO2. The impact of the 1D TiO2 synthesis reaction conditions (temperature, NaOH concentration and the TiO2 precursor concentration) on the photocatalytic H2 production rate was evaluated using a 3-factor 3-level Box Behnken design (BBD). The BBD model demonstrated that the temperature and the NaOH concentration significantly affected the 1D TiO2 phase structure, crystal size, SSA, bandgap and the photocatalytic H2 production rate. The phase structure and crystal size of 1D TiO2 were key factors affecting the H2 production rate. 1D TiO2 containing an anatase phase with a mean crystal size of 20.1±0.2 nm was synthesized at 126oC, 15 M NaOH and 49 g·L-1 TiO2. The maximum H2 production rate of 475±12 μmol·h-1 (quantum efficiency (ε) = 20.2±0.5%) for the 1D TiO2 sample was significantly enhanced when compared to commercial TiO2 P25. The H2 production rate for the optimized 1D TiO2 was significantly enhanced by decorating the structure with Pt and Au. Hydrothermal synthesized of 1D TiO2 provided an efficient and low cost method for producing H2 from ethanol, methanol, formic acid and 1,2,3 propanetriol.
关键词： hydrogen production,hydrothermal,1D titanium dioxide,TiO2-B,anatase,photocatalyst,quantum yield
更新于2025-09-23 15:23:52
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Snowflake-like Cu2S/Zn0.5Cd0.5S p–n heterojunction photocatalyst for enhanced visible light photocatalytic H2 evolution activity
摘要： Building a p–n heterojunction can accelerate the separation and transfer of photoinduced charges, which is considered to be a promising approach to constructing photocatalysts with excellent H2 evolution activities. Herein, novel snowflake-like Cu2S/Zn0.5Cd0.5S heterojunction photocatalysts were successfully synthesized. Compared to the pure Cu2S and Zn0.5Cd0.5S, the as-synthesized Cu2S/Zn0.5Cd0.5S showed remarkably improved H2 evolution rate. Cu2S/Zn0.5Cd0.5S with a Cu2S content of 3 wt% showed the optimized H2 evolution rate of 4923.5 μmol g?1 h?1 in Na2S–Na2SO3 solutions, and the corresponding apparent quantum efficiency is 30.2% at 420 nm. The experimental results indicate that the enhanced H2 evolution rates can be attributed to the fabrication of the p–n heterojunction between Cu2S and Zn0.5Cd0.5S, effectively boosting photogenerated charge carriers separation and transfer. Moreover, a plausible mechanism was proposed.
关键词： Photocatalytic,Hydrogen production,Snowflake-like,p–n heterojunction
更新于2025-09-23 15:23:52