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One-Step Photochemical Synthesis of Transition Metal - Graphene Hybrid for Electrocatalysis
摘要： For widespread use of renewable energy such as water splitting, the development of electrocatalysts on a large-scale at a low-cost that remains safe and environmentally friendly is still a great challenge. Here, we report the use of α-aminoalkyl radicals in a one-step procedure that synthesizes transition metal nanoparticle - graphene composites via photoreduction. The organic photocatalyst 2-Methyl-1-[4-(methylthio)phenyl]-2-(morpholinyl) phenyl]-1-butanone (I-907) undergoes Norrish Type I photocleavage to generate strongly reducing α-aminoalkyl radicals, when exposed to UVA. For the first time we demonstrate its ability to reduce graphene oxide (GO) and successfully synthesize Co3O4 nanoparticles decorated on graphene (Co3O4NP-rGO). The α-aminoalkyl radicals simultaneously reduce GO and Co2+ salts which nucleates on the negatively charged GO sheets and grows to form nanoparticles. The resulting Co3O4NP-rGO showed decent catalytic activity and stability for the Oxygen Evolution Reaction (OER). Our work introduces a new and environmentally friendly synthesis procedure that can be used to produce earth abundant transition metal electrocatalysts.
关键词： photochemical synthesis,reduced graphene oxide,Graphene oxide,α-aminoalkyl radicals,water oxidation,metal nanoparticles
更新于2025-11-19 16:56:35
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Bismuth vanadate single crystal particles modified with tungsten for efficient photoeletrochemical water oxidation
摘要： Highly efficient water oxidation utilizing visible light is a crucial step in water splitting. Bismuth vanadate (BiVO4) single crystal particles have attracted much attention in water oxidation recently, owing to their outstanding physicochemical properties and exposed active facets. The performance of BiVO4 single crystal particles is generally hindered by their poor conductivity and worse charge separation. Doping BiVO4 single crystal particles with other metal elements has been considered as an efficient way to improve their conductivity, charge separation and performance. However, there are few successful reports, because structure and morphology of BiVO4 single crystal particles are easily changed by addition of impurities. Here, we present that W doped BiVO4 crystal particles were successfully achieved by developing a simple impregnation method following with a high temperature annealing process. The obtained W-BiVO4 single crystal particles exhibited improved conductivity, carrier density and thereby enhanced activity for water oxidation. The solar energy conversion of the W-BiVO4 electrode was doubled compared with the pristine one. Thus, this work opens an avenue for developing efficient single crystal particle photocatalysts.
关键词： BiVO4,Tungsten,Single crystal particles,Water oxidation
更新于2025-11-19 16:51:07
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Particle size effects of tetrahedron-shaped Ag3PO4 photocatalyst on water-oxidation activity and carrier recombination dynamics
摘要： We investigated photocatalytic water-oxidation performance of tetrahedron-shaped silver phosphate (Ag3PO4) crystals with various particle sizes. The performance was clearly influenced by the particle size. The maximum activity was found for the particle with a tetrahedron edge with 1.5 μm length, which showed the highest rate of oxygen evolution. A series of analysis against time-resolved diffuse reflection spectra of the powder samples reveals that not only carrier recombination dynamic but also photoexcited carrier density can play important roles in the water oxidation. Our finding should contribute to give one of the basic ideas when designing semiconductor photocatalysts for water splitting.
关键词： Silver phosphate,Photocatalytic water oxidation,Global analysis,Carrier dynamics
更新于2025-11-19 16:51:07
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Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation
摘要： As one of the most remarkable oxygen evolution reaction (OER) electrocatalysts, metal chalcogenides have been intensively reported due to their high OER activities during the past few decades. It has been reported that electron-chemical conversion of metal chalcogenides into oxides/hydroxides would take place after OER. However, the transition mechanism of such unstable structures, as well as the real active sites and catalytic activity during OER for these electrocatalysts, has not been understood yet, which urgently needs a direct observation for the electrocatalytic water oxidation process, especially at nano or even angstrom scale. In this research, by employing advanced Cs-corrected transmission electron microscopy (TEM), a step by step oxidational evolution of amorphous electrocatalyst CoSx into crystallized CoOOH in OER has been in situ captured: irreversible conversion of CoSx to crystallized CoOOH is initiated on the surface of electrocatalysts with a morphology change via Co(OH)2 intermediate during OER measurement, where CoOOH is confirmed as the real active species. Besides, this transition process has also been confirmed by multiple applications of X-ray photoelectron spectroscopy (XPS), in situ Fourier-transform infrared spectroscopy (FTIR) and other ex situ technologies. Moreover, based on this discovery, a high-efficiency electrocatalyst of a nitrogen-doped graphene foam (NGF) coated by CoSx has been explored through a thorough structure transformation of CoOOH. We believe this in situ and in-depth observation of structural evolution in OER measurement can provide insights into the fundamental understanding of the mechanism for OER catalysts, thus enabling the more rational design of low-cost and high-efficient electrocatalysts for water splitting.
关键词： structural evolution,XPS,in situ TEM,water oxidation,cobalt chalcogenide
更新于2025-11-14 15:27:09
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Manipulation of Charge Transport by Metallic V <sub/>13</sub> O <sub/>16</sub> Decorated on Bismuth Vanadate Photoelectrochemical Catalyst
摘要： Conductive metal oxides represent a new category of functional material with vital importance for many modern applications. The present work introduces a new conductive metal oxide V13O16, which is synthesized via a simplified photoelectrochemical procedure and decorated onto the semiconducting photocatalyst BiVO4 in controlled mass percentages ranging from 25% to 37%. Owing to its excellent conductivity and good compatibility with oxide materials, the metallic V13O16-decorated BiVO4 hybrid catalyst shows a high photocurrent density of 2.2 ± 0.2 mA cm?2 at 1.23 V versus reversible hydrogen electrode (RHE). Both experimental characterization and density functional theory calculations indicate that the superior photocurrent derives from enhanced charge separation and transfer, resulting from ohmic contact at the interface of mixed phases and superior electrical conductivity from V13O16. A Co–Pi coating on BiVO4–V13O16 further increases the photocurrent to 5.0 ± 0.5 mA cm?2 at 1.23 V versus RHE, which is among the highest reported for BiVO4-based photoelectrodes. Surface photovoltage and transient photocurrent measurements suggest a charge-transfer model in which photocurrents are enhanced by improved surface passivation, although the barrier at the Co–Pi/electrolyte interface limits the charge transfer.
关键词： charge transport,bismuth vanadate,Co–Pi passivation,water oxidation,metallic V13O16
更新于2025-09-23 15:23:52
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Introduction of oxygen vacancies into hematite in local reducing atmosphere for solar water oxidation
摘要： Sn Doping and creation of oxygen vacancies have been adopted universally to overcome the poor electric conductivity and unfavorable hole diffusion length of α-Fe2O3 photoanodes. Generally, Sn doping is realized via longitudinal migration of tin element from FTO (fluorine-doped tin oxide) substrates into α-Fe2O3 at high temperature. To introduce oxygen vacancies along with Sn into hematite for further promoting its electric conductivity, we have created a local reducing atmosphere via partial oxidation of graphite while doping hematite with Sn. The donor density of the resultant Fe2O3 photoanode annealed on graphite (G-Fe2O3) at 770 °C for 20 min is increased to ～1.7 times that of the counterpart annealed on SiO2 powders (S-Fe2O3), indicating that the electric conductivity of hematite is improved after introduction of oxygen vacancies. Moreover, oxygen vacancies have been demonstrated to significantly reduce the charge transfer resistance of Sn doped hematite. Consequently, the photocurrent density of G-Fe2O3 is enhanced remarkably (～70%) compared with S-Fe2O3. However, the improvement in photocurrent density due to oxygen vacancies becomes less significant when more Sn is doped into hematite. The strategy for creation of oxygen vacancies reported here can be extended to other photoanodes for better understanding the effect of oxygen vacancies on PEC performance.
关键词： Oxygen vacancies,Sn doping,Solar water oxidation,Hematite
更新于2025-09-23 15:23:52
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Enhanced solar light driven activity of p-n heterojunction for water oxidation induced by deposition of Cu2O on Bi2O3 microplates
摘要： As an important half reaction in solar-driven water splitting, it is more challenging to develop low-cost and highly efficient photocatalysts for water oxidation. The enhancement of sunlight harvesting and inhibition of charge-carrier recombination are keys to fabricating efficient semiconductor-based photocatalysts for energy conversion from solar light to chemicals. Herein, we reported highly dispersive Cu2O/Bi2O3 composites prepared by a facile and benign synthetic route, where n-type Bi2O3 microplates and nano-sized p-type Cu2O were coupled together to construct heterojunctions to improve the transportation efficiency of photoinduced charge carriers, benefited from the intimate interactions at the interfaces between Bi2O3 and Cu2O. The electrochemical properties of charge-transportation and population of charge carriers were investigated in the heterojunctions. The hybrid materials exhibit both enhanced photocatalytic performances in water oxidation and photodegradation of dyes compared with sole Bi2O3 or Cu2O under artificial solar light irradiation. The initial O2 evolution rate of the heterojunction system is 1.4- and 8-fold higher than the pure Bi2O3 and Cu2O, respectively. This study provides new protocols for synthesizing novel hybrid materials with insights into heterojunction-based photocatalysis for green energy production and wastewater purification.
关键词： Nanocomposite,Water oxidation,Photocatalysis,Heterojunction,Wastewater purification
更新于2025-09-23 15:23:52
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Mixed-metal organic framework-coated ZnO nanowires array for efficient photoelectrochemical water oxidation
摘要： Designing of high-performance photoanodes is essential for efficient solar energy conversion in photoelectrochemical (PEC) water splitting. Herein, we report an effective approach to synthesize three dimensional (3D) mixed-metal organic framework-coated ZnO nanowires array (ZnNi MOF@ZnO) for the effective PEC performance. The ZnO nanowires act as photon absorber as well as rapid charge transporter; whilst the ZnNi MOF provides the active sites for PEC process by lowering the energy barrier of water oxidation and suppressing electron-hole recombination. The 3D nanostructure of ZnNi MOF@ZnO nanowires array provides intimate interfacial contact through covalent interactions between the ZnNi MOF and ZnO nanowires which facilitates the rapid charge transfer during photocatalytic oxygen evolution reactions. As a result, the ZnNi MOF@ZnO nanowires array exhibited excellent photoelectrochemical water oxidation with very low onset potential (0.31 V vs. RHE) and high photocurrent density (1.40 mA/cm2) as compared to the Zn MOF @ZnO and ZnO nanowires array. This facile strategy provides a promising direction towards high performance photoanode design for adequate solar energy conversion.
关键词： Metal organic frameworks (MOFs),Photoelectrocatalyst,Nanowires array,Photoelectrochemical water oxidation,Photoanodes
更新于2025-09-23 15:22:29
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Study on supercritical water oxidation of o-dichlorobenzene in a quartz micro-reactor with in situ microscope and Raman spectroscopy
摘要： The supercritical water oxidation (SCWO) of o-dichlorobenzene (o-DCB) in a fused quartz capillary reactor was studied by in situ microscope combined with Raman spectroscopy. The influence of oxidant dosage, reaction temperature and time on the o-DCB degradation efficiency was investigated and the reaction kinetics for CO2 yield was explored as well. The obvious phase change of o-DCB-H2O/H2O2 system was observed during the heating and cooling process. The increase in H2O2 dosage, temperature and time enhanced the o-DCB degradation efficiency. The degradation of o-DCB could be attributed to the simultaneous oxidation induced by HO· and O2. The effect of temperature on the o-DCB degradation efficiency and the CO2 yield was not significant at the lower temperature stage but turned to be important at the higher temperature stage. When the oxidant dosage was twice that of chemometry and the temperature and time were 440.0 °C and 4 min, respectively, the o-DCB degradation efficiency reached approximately 100%. Under the same conditions, the CO2 yield was lower than the o-DCB degradation efficiency, indicating that the degradation of o-DCB was a multi-step reaction. The reaction kinetics showed that the kinetics of CO2 production in SCWO followed the pseudo-first order and the apparent activation energy was 172.4 kJ mol?1.
关键词： Microscope,Supercritical water oxidation,O-dichlorobenzene,Fused quartz micro-reactor,Raman spectroscopic
更新于2025-09-23 15:22:29
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Synthesis of oxygen deficient bismuth oxide photocatalyst for improved photoelectrochemical applications
摘要： The present paper reports the effect of nitrogen modification on photoelectrochemical (PEC) water oxidation behavior of Bi2O3 semiconductor thin film. The semiconductor particles were synthesized via hydrothermal route using Bi(NO3)3 as a Bi3+ ion precursor and urea as the nitrogen source followed by drop-cast the particles and annealing the film at 600oC. The synthesized Bi2O3 exhibited band gap energy of 3.01 eV, calculated from the UV-vis absorption spectrum which decreases to 2.75eV through N-modification. Water oxidation behavior of the material has been tested through linear sweep voltammetry under periodic illumination. Highest photo-current of 180 μAcm-2 has been measured for water oxidation reaction at 0.95V vs. Ag/AgCl, under illumination of 35mWcm-2. N-incorporation can enhance the photocurrent up to 50% whereas the visible responsiveness of the material improves significantly as confirmed from electrochemical action spectra and UV-visible absorption spectra. The photocatalytic activity of the semiconductor particles was confirmed through decoloration of Rhodamine-B dye, by spectrophotometric measurements.
关键词： Hydrothermal synthesis,Oxygen vacancies,Bismuth oxide photocatalyst,PEC water oxidation.,N-modification
更新于2025-09-23 15:22:29