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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Hole transfer layer of glucose-derived carbon enabled rapid charge transfer and hole storage for efficient water splitting

Sicheng Zhang,Tengfei Duan,Dejian Yan,Hongyun Yang,Lingling Cheng,Yong Pei,Kuiyi You,He'an Luo

Charge recombination at the interface of oxygen evolution catalyst (OEC) and BiVO 4 -based photoanode is one of the great challenges to achieve efficient photoelectrochemical (PEC) water splitting due to the poor charge transfer and separation efficiency of BiVO 4 . Herein, a composite photoanode (NiFe/C-Mo:BiVO 4 ) consisting of a molybdenum doped BiVO 4 photoanode, an OEC interfacial layer of NiFeOOH and a tailorable hole transfer layer (HTL) made of glucose-derived carbon in between, was designed and fabricated for highly efficient PEC water splitting. The composite NiFe/C-Mo:BiVO 4 photoanode exhibited the photocurrent density of 5.62 mA cm −2 at 1.23 V RHE and an outstanding photo-stability. Characterization and photoelectrochemical analyses revealed that the inserted carbon HTL, though not active for surface water oxidation kinetics, greatly suppressed the unwanted recombination of electron-hole pairs and drastically improved the transfer and storage of charge carriers at the OEC/BiVO 4 interface. A surface charge separation efficiency of 89 % at 1.23 V RHE and remarkable hole storage properties were obtained. This work afforded a novel approach to the design of low-cost and sustainable HTL integrated photoanodes for efficient PEC water oxidation.

CAS / MDL: 17524-05-9 10043-35-3
研究领域: 材料科学 · 能源科学
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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Construction of MIL-88(Fe) derived MOF/TiO2 photoanode for efficient photoelectrochemical water splitting

Wenjin Ni,Sicheng Zhang,Lingling Cheng,Tiejun Luo,Hongyun Yang,Tengfei Duan,Dejian Yan

Developing efficient photoanodes for water oxidation is highly promising due to their critical role in producing green H 2 and harnessing solar energy. Herein, a metal-organic framework (MOF)/photoanode was successfully constructed by coating TiO 2 nanorods with MIL-88(Fe) MOF for photoelectrochemical (PEC) water splitting. The results demonstrated that MIL-88(Fe) was uniformly and tightly coated on TiO 2 and functioned as a cocatalyst. The MIL-88(Fe) MOF provides a large surface area and more Fe-O active sites, contributing to high PEC activity by reducing electron/hole recombination and enhancing light response capability. Moreover, the photoanode also exhibited an improved charge conductivity. As a result, the MIL-88(Fe)/TiO 2 photoanode exhibited an excellent photocurrent density of 1.06 mA cm −2 at 1.23 V RHE , which is approximately 2.6 times higher than the pristine TiO 2 . Charge transfer kinetics analyses and electrochemical tests were carried out and revealed that the improved PEC performance was attributed to the introduction of MIL-88(Fe), which promoted charge separation-transfer. This research provided new insights into the design of efficient semiconductor/MOF composite photoanodes for PEC water oxidation.

研究领域: 材料科学 · 能源科学
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Polymers · 2021 ·Vol. 13 ·期 19 ·3341 · IF 4.329

An Electrospun Porous CuBi2O4 Nanofiber Photocathode for Efficient Solar Water Splitting

Xiuhua Yuan,Yeling Liu,Hui Yuan,Bingxin Liu,Tianyu Guo,Huawei Zhou,Xia Li

While the CuBi2O4-based photocathode has emerged as an ideal candidate for photoelectrochemical water splitting, it is still far from its theoretical values due to poor charge carrier transport, poor electron–hole separation, and instability caused by self-photoelectric-corrosion with electrolytes. Establishing synthesis methods to produce a CuBi2O4photocathode with sufficient cocatalyst sites would be highly beneficial for water splitting. Here, the platinum-enriched porous CuBi2O4nanofiber (CuBi2O4/Pt) with uniform coverage and high surface area was prepared as a photocathode through an electrospinning and electrodeposition process for water splitting. The prepared photocathode material was composed of a CuBi2O4nanofiber array, which has a freestanding porous structure, and the Pt nanoparticle is firmly embedded on the rough surface. The highly porous nanofiber structures allow the cocatalyst (Pt) better alignment on the surface of CuBi2O4, which can effectively suppress the electron–hole recombination at the electrolyte interface. The as-fabricated CuBi2O4nanofiber has a tetragonal crystal structure, and its band gap was determined to be 1.8 eV. The self-supporting porous structure and electrocatalytic activity of Pt can effectively promote the separation of electron–hole pairs, thus obtaining high photocurrent density (0.21 mA/cm2at 0.6 V vs. RHE) and incident photon-to-current conversion efficiency (IPCE, 4% at 380 nm). This work shows a new view for integrating an amount of Pt nanoparticles with CuBi2O4nanofibers and demonstrates the synergistic effect of cocatalysts for future solar water splitting.Keywords:electrospinning;CuBi2O4nanofiber;photocathode;water splitting

研究领域: 材料科学 · 能源科学
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Journal of Materials Chemistry A · 2022 ·Vol. 11 ·期 1 ·149-157 · IF 14.511

In situ surface-trap passivation of CuBi2O4 photocathodes for unbiased solar water splitting

Yingfei Hu,Jun Wang,Huiting Huang,Jianyong Feng,Wangxi Liu,Hangmin Guan,Lingyun Hao,Zhaosheng Li,Zhigang Zou

Passivating surface traps plays a crucial role in mitigating the efficiency loss of solar water-splitting electrodes. However, the associated surface-trap passivation approaches require the introduction of an overlayer, complicating the fabrication process and increasing the capital cost of photoelectrodes. Herein, using CuBi2O4 as a prototype, an in situ surface-trap passivation strategy is developed, which yields a beneficial 90 mV anodic shift in hydrogen-evolution onset. Detailed mechanism investigations prove that the intentionally added Mg2+ ions in the precursor gradually segregate as MgO and enrich at the grain boundaries/surface of the CuBi2O4 multicrystalline, porous film during annealing, via which surface traps stemming from dangling bonds are spontaneously passivated; measurements of photovoltage generation characteristics and carrier lifetime validate the favorable roles of the MgO passivator in CuBi2O4 photocathodes. A bias-free water-splitting device is assembled using MgO-passivated CuBi2O4 and Mo-doped BiVO4 as the photocathode and photoanode respectively in a tandem configuration, delivering a solar-to-hydrogen conversion efficiency of approximately 0.41%.

CAS / MDL: 2408-70-0
研究领域: 材料科学 · 能源科学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2018 · IF 11.698

Amorphous Ta2OxNy-enwrapped TiO2 rutile nanorods for enhanced solar photoelectrochemical water splitting

Hongwen Zhang,Lei Ma,Jintao Ming,Bingqian Liu,Yibo Zhao,Yidong Hou,Zhengxin Ding,Chao Xu,Zizhong Zhang,Jinlin Long

This work demonstrated the 12 fold-enhanced solar water splitting over the type-II core-shell nanostructured TiO 2 rutile photoanodes by orienting the charge flow and accelerating the hole transport to water-oxidation sites. Such nanoheterostructured photoanodes were designed rationally and prepared by a facile strategy to enwrapping an amorphous Ta 2 O x N y layer on surface of TiO 2 nanorods grown on the FTO glass substrates, consequently the incident photon-to-current conversion efficiency was increased from 2.2% to 22.6% in a two-electrode system under 390 nm light irradiation. The activity results showed that under AM 1.5 G illumination, the photocurrent output of TiO 2 @Ta 2 O x N y photoanodes reached a stable density of 1.32 mA cm −2 at 1.23 V vs RHE, and which is 12 times and ca. 4.3 times than that of the pristine TiO 2 and TiO 2 @Ta 2 O 5 counterparts, respectively. Correspondingly, the oxygen evolution rate was improved from 20.3 to 112.7 mmol m −2  h −1 . A solar-to-chemical energy conversion efficiency of ca. 1.49% was achieved at 1.23 V vs RHE.

研究领域: 材料科学 · 能源科学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

P–N homojunction and heteroatom active site engineering over Fe2O3 nanorods for highly efficient photoelectrochemical water splitting

Huanhuan Wu,Huihui Ding,Jun Ma,Xiang Li,Shuangshuang Huai,Chengming Zhang,Ping Li,Jingjing Xia,Xiaolong Fang,Xiufang Wang

Limited charge transfer and slow oxygen evolution (OER) kinetics significantly impede the practical realization of photoanodes for photoelectrochemical (PEC) water splitting. Here, pn-type-Fe 2 O 3 homojunction photoanode catalysts with P active sites are designed by doping phosphorus (P) into outer lattice of n-type Fe 2 O 3 nanorods (pn-P-Fe 2 O 3 ). The optimized pn-P-Fe 2 O 3 photoanode shows the maximum photocurrent density of 2.61 mA/cm 2 at 1.23 V RHE , and the value is 6.4 times greater than that of pristine Fe 2 O 3 . Experimental and theoretical results clearly show that the P–N homogeneous junctions constructed in Fe 2 O 3 through P-doping increase active sites for H 2 O adsorption and activation, reduce OER reaction energy barrier, and promote effective separation of photogenerated electron-hole pairs and water splitting kinetics. This not only makes the photoelectric water decomposition performance outstanding, but also produces excellent durability. This work provides a novel simple and environmentally friendly strategy for designing effective photoanodes for PEC water splitting.

研究领域: 材料科学 · 能源化学
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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING · 2025 · IF 4.6

Characterization and properties of polypyrrole modified ZnIn2S4/TiO2/Ti photoanode in photocatalytic fuel cell

Yunlan Xu,Jiaxin Mou,Lin Dong,Qingmei Qiao,Dengjie Zhong

The performance of photocatalytic fuel cell (PFC) depends on photoanode, which is the key to generate photoexcited carriers and degrade organic wastes. In this study, ZnIn 2 S 4 nano-bandgap semiconductor and polypyrrole were used to modify TiO 2 to prepare polypyrrole/ZnIn 2 S 4 /TiO 2 /Ti photoanode to increase its photo-response range and the separation of photoexcited carriers. The PFC with polypyrrole/ZnIn 2 S 4 /TiO 2 /Ti photoanode and copper cathode was built to degrade RhB and generate electricity. The RhB removal rate, open-circuit voltage, short-circuit current density, and maximum power density of the photocatalytic fuel cell were 94.6 % (1 h), 0.47 V, 0.23 mA cm −2 and 21.11 μW cm −2 , respectively. The improvement of PFC performance is attributed to the good visible-light responsive properties of polypyrrole/ZnIn 2 S 4 .The presence of polypyrrole acts as both an electron donor and a hole acceptor, which provides an ideal pathway for the separation and transmission of photogenerated carriers. The synergistic effect of polypyrrole, ZnIn 2 S 4 and TiO 2 eventually increases the photocatalytic ability of the PFC. This research can offer reference for the study of TiO 2 -based efficient visible light responsive PFC.

研究领域: 材料科学 · 环境科学
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Nanomaterials · 2022 ·Vol. 12 ·期 19 ·3444 · IF 5.719

A Simple Fabrication of Sb2S3/TiO2 Photo-Anode with Long Wavelength Visible Light Absorption for Efficient Photoelectrochemical Water Oxidation

Fei Han,Sai Ma,Dong Li,Md Mofasserul Alam,Zeheng Yang

An Sb2S3-sensitized TiO2(Sb2S3/TiO2) photo-anode (PA) exhibiting a high photo-electrochemical (PEC) performance in water oxidation has been successfully prepared by a simple chemical bath deposition (CBD) technique. Herein, the Raman spectra and XPS spectrum of Sb2S3/TiO2confirmed the formation of Sb2S3on the TiO2coatings. The Sb2S3/TiO2photo-anode significantly shifted the absorption edge from 395 nm (3.10 eV) to 650 nm (1.90 eV). Furthermore, the Sb2S3/TiO2photo-anode generated a photo-anodic current under visible light irradiation below 650 nm due to the photo-electrochemical action compared with the TiO2photo-anode at 390 nm. The incident photon-to-current conversion efficiency (IPCE = 7.7%) at 400 nm and −0.3 V vs. Ag/AgCl was 37 times higher than that (0.21%) of the TiO2photo-anodes due to the low recombination rate and acceleration of the carriers of Sb2S3/TiO2. Moreover, the photo-anodic current and photostability of the Sb2S3/TiO2photo-anodes improved via adding the Co2+ions to the electrolyte solution during photo-electrocatalysis.Keywords:Sb2S3/TiO2;photo-anode;long wavelength;photo-electrochemical;water oxidation

研究领域: 材料科学 · 能源科学
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WATER RESEARCH · 2021 · IF 11.236

Intermediate accumulation and toxicity reduction during the selective photoelectrochemical process of atrazine in complex water bodies

Baoling Niu,Junzhuo Cai,Wenjing Song,Guohua Zhao

Selective removal of atrazine (ATZ) in wastewater and clarification of the degradation intermediate-toxicity correlation are of great importance. A newly molecularly imprinted, {001} facets-exposed TiO 2 (MI-TiO 2,001 ) photoanode with strong catalytic and selective ability was designed. ATZ was selectively removed from pesticide wastewater, reaching 1.9 µg L −1 , approximately 1/10 of the concentration achieved with nonselective treatment. This selective removal originated from the preferential adsorption and enrichment of ATZ onto MI-TiO 2,001 . The highly specific recognition relied on the halogen bond and strong hydrogen bond formed between the Cl atom and triazine ring π orbital of ATZ and the surface -OH group of MI-TiO 2,001 as well as the recognition of MI-TiO 2,001 to the shape and size of ATZ. The specific interaction leads to different accumulations of intermediates. The correlation of intermediate and toxicity was also discussed. Aquatic toxicity was rapidly reduced through the direct dealkylation path, and due to the accumulation of highly toxic 2‑hydroxy-4-ethylamino-6-isopropylamino-s-triazine, there will be transient fluctuations via the dechlorination-hydroxylation path first. The final product was identified as nearly nontoxic cyanuric acid, the selective accumulation of which indicated that there was almost 100% removal of aquatic toxicity and cytotoxicity with only 9.8% removal of total organic carbon. This work provides new insight into the correlation of pollutant degradation intermediates and changes in toxicity.

CAS / MDL: 5593-70-4 9022-96-2
研究领域: 环境科学 · 化学工程 · 毒理学
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Catalysis Science & Technology · 2023 ·Vol. 13 ·期 24 ·7046-7058 · IF 5

TiO2 spatially confined growth of Sb2(S,Se)3@TiO2 NT heterojunction photoanodes and their photoelectrochemical properties

Wei Jin,Dekang Liu,Liyuan Zhang,Qian Sun,Yishan Wang,Enzhou Liu,Xiaoyun Hu,Hui Miao

Titanium dioxide (TiO2), a conventional n-type semiconductor, was widely used in photocatalysis, electrocatalysis and photoelectrocatalysis due to its good UV absorption and stable physical and chemical properties. However, its wide band gap and low oxygen reaction (OER) activity limited its application in photoelectrochemical (PEC) water splitting. In this work, we successfully constructed type-II Sb2(S,Se)3@TiO2 core–shell heterojunctions. Antimony sulfide selenide (Sb2(S,Se)3) was a quasi-one-dimensional light-absorbing material with an adjustable band gap (1.1–1.8 eV), which broadened the TiO2 light absorption range and effectively promoted the photogenerated carrier separation, transportation and utilization. Of particular note, novel Sb2(S,Se)3 nanospheres (NSPs) (ca. 69 nm) were in situ grown inside the tubes attributed to the unique space-confinement effect of TiO2 nanotubes (NTs). The IPCE value for Sb2(S,Se)3@TiO2 at 734 nm was 10.808% compared to 0.030% for TiO2. The separation efficiency and injection efficiency increased from 2.48% and 31.62% to 4.90% and 36.48%, respectively. The onset potential was moved negatively by 60 mV, and the maximum photocurrent density of 1.53 mA cm−2 at 1.23 V vs. RHE was 13.9 times higher than that of TiO2 (0.11 mA cm−2). This work provided a new idea for the application of TiO2 in the field of PEC water splitting.

研究领域: 材料科学 · 能源科学
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NANOTECHNOLOGY · 2017 ·Vol. 28 ·期 39 ·394003 · IF 3.44

Improved charge separation efficiency of hematite photoanodes by coating an ultrathin p-type LaFeO3 overlayer

Tao Fang,Yongsheng Guo,Songhua Cai,Ningsi Zhang,Yingfei Hu,Shiying Zhang,Zhaosheng Li,Zhigang Zou

Many metal-oxide candidates for photoelectrochemical water splitting exhibit localized small polaron carrier conduction. Especially hematite (α-Fe2O3) photoanodes often suffer from low carrier mobility, which causes the serious bulk electron-hole recombination and greatly limits their PEC performances. In this study, the charge separation efficiency of hematite was enhanced greatly by coating an ultrathin p-type LaFeO3 overlayer. Compared to the hematite photoanodes, the solar water splitting photocurrent of the Fe2O3/LaFeO3 n–p junction exhibits a 90% increase at 1.23 V versus the reversible hydrogen electrode, due to enlarging the band bending and expanding the depletion layer.

研究领域: 材料科学 · 光电化学
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CATALYSIS LETTERS · 2020 ·Vol. 151 ·期 5 ·1231-1238 · IF 2.482

Efficient Improved Charge Separation of FeP Decorated Worm-Like Nanoporous BiVO4 Photoanodes for Solar-Driven Water Splitting

Ge Jianhua,Ding Xiulong,Jiang Daochuan,Zhang Lei,Du Pingwu

Abstract Photoelectrochemical (PEC) water splitting using BiVO 4 semiconductor photoanodes have been appealed to plenty of attentions in the past few decades. In this study, FeP was used as an active precious-metal-free cocatalyst for the first time to enhance the performance of worm-like nanoporous BiVO 4 photoanodes for PEC water splitting. Characterization results demonstrate that FeP nanoparticles were successfully deposited on surface of the pritine BiVO 4 photoanodes, and served as an noble metal-free cocatalyst for solar-driven PEC water splitting. Furthermore, a maximum photocurrent density of ~ 3.05 mA/cm 2 at 1.23 V vs RHE could be achieved by loading moderate amount of FeP on the surface of BiVO 4 , which is about 1.6 times higher than that of the unmodified BiVO 4 . Meanwhile, the efficient suppression of surface recombination by FeP was also confirmed by the PEC measurements in Na 2 SO 3 solution. The maximum ABPE of FeP/BiVO 4 photoanodes was ~ 0.53% at 0.60 V vs RHE, indicating the potential application for overall solar-driven water splitting. Graphic Abstract

研究领域: 材料科学 · 能源科学
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