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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2023 · IF 10.9

Amorphous high-entropy phosphoxides for efficient overall alkaline water/seawater splitting

Han-Ming Zhang,Lihao Zuo,Yuhang Gao,Junxia Guo,Caizhen Zhu,Jian Xu,Jinfeng Sun

Designing and synthesizing cost-effective bifunctional catalysts for overall alkaline water/seawater splitting is still a huge challenge for hydrogen production. Herein, Co/Ni/Fe/Mn based-amorphous high-entropy phosphoxide self-standing electrode (CNFMPO) is synthesized by the facile and fast electrodeposition method. CNFMPO exhibits excellent bifunctional electrocatalytic performances on alkaline water/seawater electrolysis. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of CNFMPO in alkaline water/seawater are as low as 43/73 and 252/282 mV to reach a current density of 10 mA cm −2 , respectively. Additionally, two-electrode electrolyzers with CNFMPO||CNFMPO successfully achieve the current density of 10 mA cm −2 at low voltages of 1.54 and 1.56 V for overall alkaline water/seawater splitting, respectively. CNFMPO exhibits satisfactory long-term stability on overall alkaline water/seawater splitting for the surface reconstruction into active metal hydroxide/(oxy)hydroxide, phosphite, and phosphate. Moreover, no hypochlorite is detected during seawater electrolysis for the beneficial chlorite oxidation inhibition of the reconstructed phosphite and phosphate. The excellent catalytic performances of CNFMPO are due to the unique amorphous structure, multi-component synergistic effect, beneficial electronic structure modulation, and surface reconstruction during the catalytic reaction process. Therefore, CNFMPO has shown potential promotion to the development of the water/seawater splitting industry as a promising substituent for noble-metal electrocatalysts. This work provides new insights into the design of efficient bifunctional catalysts for overall water/seawater splitting.

研究领域: 材料科学 · 能源化学 · 电化学
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Chemical Science · 2018 ·Vol. 9 ·期 21 ·4746-4755 · IF 9.063

Trapping [PMo12O40]3− clusters into pre-synthesized ZIF-67 toward MoxCoxC particles confined in uniform carbon polyhedrons for efficient overall water splitting

Congfang Chen,Aiping Wu,Haijing Yan,Yinglu Xiao,Chungui Tian,Honggang Fu

Bi-transition metal carbides (BTMCs) are promising in catalytic fields, but the synthesis of small-sized BTMCs remains a challenge. Here, MoxCoxC (mainly below 20 nm in size) confined in uniform carbon polyhedrons (MoxCoxC@C) was synthesized based on trapping [PMo12O40]3− (PMo12) clusters into pre-synthesized, uniform ZIF-67 (PMo/ZIF-67). The opening of the windows (0.34 nm) of ZIF-67 cages through heating is essential to allow the trapping of PMo12 into the cages. This trapping route provides a new method to successfully combine POMs and MOFs that can not be effectively combined via traditional POMOF-based (simultaneous assembly) routes. It also has advantages in controlling the uniformity and components of the materials. The size matching of PMo12 (1 nm) and the cages (1.16 nm) of ZIF-67 enables effective contact of the Co and Mo sources, thus giving small-sized MoxCoxC protected by carbon via calcination. The optimized catalysts showed good performance for water splitting with a low η10 of 83 mV (295 mV) for the hydrogen (oxygen) evolution reaction, which is superior to those derived from ZIF-67 and precursors from POMOF-based routes. Our results also indicated that the HER activity is determined by the kind of BTMC, and the activity for the OER is relative to the oxygen-containing species formed during the initial OER test.

研究领域: 材料科学 · 催化化学
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ACS Catalysis · 2022 · IF 13.7

Ge-Doped Cobalt Oxide for Electrocatalytic and Photocatalytic Water Splitting

Weiqi Guo,Haolin Luo,Zhi Jiang,Dongxu Fang,Jiasheng Chi,Wenfeng Shangguan,Zhiliang Wang,Lianzhou Wang,Adam F. Lee

Cobalt oxides find widespread application in energy materials as oxygen evolution catalysts (OECs) in the oxygen evolution reaction (OER) and photocatalytic overall water splitting (OWS) reaction. However, the nature of the active cobalt species, their role in these reactions, and possible commonalities remain poorly understand. Here, the impact of (redox-inert) germanium dopants on the physicochemical properties of Co3O4 nanoparticles was investigated in electrochemical oxygen evolution and photocatalytic OWS reactions. A significant enhancement in OER performance on doping is attributed to the restructuring of spinel Co3O4 to serpentine Co3Ge2(OH)5, with the latter transforming to an oxyhydroxide active phase during OER. Combination of the p-type Co3Ge2(OH)5 semiconductor as an OEC with an n-type Bi0.5Y0.5VO4 semiconductor doubles the photocatalytic OWS activity of the latter, resulting in H2 and O2 productivities of ∼175.7 and ∼90.1 μmol/h, respectively. Formation of the composite semiconductor induces an intense internal electric field across the p–n junction, facilitating separation of photogenerated carriers and increased OWS activity, which is also validated in alternative photocatalyst, Al-doped SrTiO3. A similar transformation of serpentine Co3Ge2(OH)5 to an oxyhydroxide was not observed during OWS, indicating that Ge doping confers distinct advantages for electrochemical OER vs photocatalytic OWS.

研究领域: 材料科学 · 电化学 · 光化学 · 催化 · 能源材料
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JOURNAL OF MATERIALS CHEMISTRY · 2012 ·Vol. 22 ·期 42 ·22619-22623 · IF 5.968

A facile route to (ZnS)x(CuInS2)1−x hierarchical microspheres with excellent water-splitting ability

Yuhan Lin,Fang Zhang,Daocheng Pan

A series of (ZnS)x(CuInS2)1−x hierarchical micro/nano-structured solid solutions with precisely controlled chemical composition were synthesized via a facile one-pot solvothermal method. ZnO, Cu2O, and In(OH)3 are used as the starting materials and dissolved in ethanol dithiocarbamic acid which is formed from CS2 and ethanolamine in situ. The ethanol dithiocarbamic acid not only serves as a thermally-degradable ligand, but also acts as sulfur source during synthesis, and can be completely removed by a simple calcination process. As-prepared (ZnS)x(CuInS2)1−x microspheres have a hierarchical micro/nano structure composed of around 7 nm nanoparticles. These samples show excellent photocatalytic H2 evolution activity under visible-light irradiation without any noble metal loading owing to their high surface area (as high as 101.6 m2 g−1) and unique hierarchical structure.

研究领域: 材料科学 · 能源化学
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Energy Material Advances · 2022 · IF 0

Growth of BaTaO2N–BaNa0.25Ta0.75O3 Solid Solution Photocatalyst for Visible Light-Driven Z-Scheme Overall Water Splitting

Ying Luo,Qiaoqi Guo,Jun Xu,Hanghang Zhou,Zheng Wang,Hong He

BaTaO2N with intense visible light absorption has been demonstrated as a promising photocatalyst for Z-scheme overall water splitting, whereas the photocatalytic activity of BaTaO2N is still restricted by strong charge recombination at structural defects. Here, we present the direct growth of BaTaO2N–BaNa0.25Ta0.75O3 solid solution from a lattice-matched BaNa0.25Ta0.75O3 precursor through volatilization of Na species during a nitridation process. This method promotes the direct phase transformation from BaNa0.25Ta0.75O3 to BaTaO2N to inhibit the formation of defect states. As a result, the as-obtained BaTaO2N–BaNa0.25Ta0.75O3 solid solution shows greatly enhanced activity compared to the conventional BaTaO2N, regardless of photocatalytic H2 evolution in the presence of methanol or Z-scheme overall water splitting. This study provides a facile method to construct (oxy)nitride-based solid solution photocatalysts with low defect density for efficient solar hydrogen production from water splitting.

研究领域: 材料科学 · 能源化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Vacancy-rich heterogeneous MnCo2O4.5@NiS electrocatalyst for highly efficient overall water splitting

Xingxing Zhu,Zhengtong Ji,Wubin Wan,Yongfu Zhu,Xingyou Lang,Qing Jiang

Alkaline water electrolysis is regarded as a promising technology for sustainable energy conversion. Spinel oxides have attracted considerable attention as potential catalysts because of their diverse metal valence states. However, achieving the required current densities at low voltages is a challenge due to its limited active sites and suboptimal electron transport. In this study, we present a novel bifunctional catalyst composed of MnCo 2 O 4.5 nanoneedles grown on NiS nanosheets for water electrolysis. Remarkably, MnCo 2 O 4.5 @NiS demonstrates exceptional catalytic activity, requiring 187 and 288 mV to achieve a current density of 100 mA cm −2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. The impressive performance of MnCo 2 O 4.5 @NiS is demonstrated by the lower value of voltage 1.44 V needed to deliver the current density of 10 mA cm −2 , which outperformed the 1.66 V required for a commercial Pt/C||RuO 2 system. Detailed structure analysis and density functional theory (DFT) calculations reveal that the MnCo 2 O 4.5 @NiS heterostructure enhances electron transfer at the interface, promotes the formation of oxygen vacancies and tunes the electronic structures of Mn and Co. These findings underscore the potential of MnCo 2 O 4.5 @NiS as an efficient and cost-effective electrocatalyst for hydrogen production.

研究领域: 材料科学 · 能源化学
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MOLECULES · 2024 ·Vol. 29 ·期 5 ·951 · IF 4.2

Interfacial Interaction in NiFe LDH/NiS2/VS2 for Enhanced Electrocatalytic Water Splitting

Tingxia Wang,Xu Zhang,Xiaojiao Yu,Junpeng Li,Kai Wang,Jinfen Niu

A bifunctional electrocatalyst with high efficiency and low costs for overall water splitting is critical to achieving a green hydrogen economy and coping with the energy crisis. However, developing robust electrocatalysts still faces huge challenges, owing to unsatisfactory electron transfer and inherent activity. Herein, NiFe LDH/NiS2/VS2heterojunctions have been designed as freestanding bifunctional electrocatalysts to split water, exhibiting enhanced electron transfer and abundant catalytic sites. The optimum NiFe LDH/NiS2/VS2electrocatalyst exhibits a small overpotential of 380 mV at 10 mA cm−2for overall water splitting and superior electrocatalytic performance in both hydrogen and oxygen evolution reactions (HER/OER). Specifically, the electrocatalyst requires overpotentials of 76 and 286 mV at 10 mA cm−2for HER and OER, respectively, in alkaline electrolytes, which originate from the synergistic interaction among the facilitated electron transfer and increasingly exposed active sites due to the modulation of interfaces and construction of heterojunctions.

CAS / MDL: 62-55-5
研究领域: 材料科学 · 能源化学
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PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE · 2021 ·Vol. 218 ·期 22 ·2100377 · IF 1.981

2D Nanosheets of Mo2C/CoMoS4 as Active Electrocatalyst for Water Splitting

Pan Liu,Sumin Wang,Yufei Quan,Zhiruo Shen,Qiguan Wang

2D composited nanosheets of Mo 2 C/CoMoS 4 are synthesized by a hydrothermal approach to obtain a bifunctional water-splitting electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in aqueous alkaline solution. Due to the richened defects formed on the 2D catalyst, the as-derived Mo 2 C/CoMoS 4 exhibits high activity. At 10 mA cm −2 , the HER and OER overpotentials of the 2D Mo 2 C/CoMoS 4 nanosheets are just 117 and 250 mV, respectively, with the corresponding Tafel slope of 90 and 75 mV dec −1 , near to the commercial Pt/C and IrO 2 . X-ray photoelectron spectroscopy proves the strong interactions between Mo 2 C and CoMoS 4 and the Raman analysis certifies the presence of richened defects in Mo 2 C/CoMoS 4 . Moreover, the Mo 2 C/CoMoS 4 possesses a long-term catalytic stability, showing potential application in the water splitting.

CAS / MDL: 15060-55-6 25155-30-0
研究领域: 材料科学 · 电化学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2021 · IF 5.816

2D/3D WO3/BiVO4 heterostructures for efficient photoelectrocatalytic water splitting

Peicheng Wei,Yan Wen,Kaifeng Lin,Xin Li

Developing novel photoanodes with high efficiency for photoelectrochemical (PEC) water splitting has become the key to solar energy conversion and storage realm. Herein, 3D worm-like bismuth vanadate (BiVO 4 ) is grafted on 2D thin tungsten trioxide (WO 3 ) underlayer by electrodeposition to form mixed–dimensional structured photoanode, resulting in significant improvement of the photocatalytic performance and the charge separation efficiency. Characterization results prove that the mixed–dimensional structured can boost the photocatalytic activity by suppressing back reaction and charge recombination of the bulk BiVO 4 . Simultaneously, the electrical conductivity of photoanode can be increased by W 6+ doping. Furthermore, a robust catalyst NiCo 2 O x is coated onto the surface of WO 3 /BiVO 4 photoanode, exhibiting a desirable photocurrent of 3.85 mA cm −2 at 1.23 V vs . RHE and an excellent stability over 3 h. Both the excellent photocurrent density and great operational stability of this 2D/3D WO 3 /BiVO 4 photoanode make it a promising material for practical applications.

研究领域: 材料科学 · 能源转换与存储
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ELECTROCHIMICA ACTA · 2021 · IF 6.901

Ultrathin Ti2NTx MXene-wrapped MOF-derived CoP frameworks towards hydrogen evolution and water oxidation

Hui Zong,Ruijuan Qi,Ke Yu,Ziqiang Zhu

Hydrogen evolution is of great significance for reducing carbon emissions and realizing carbon-neutral. Hydrogen evolution reaction (HER) by water splitting has no carbon emissions and pollution, but it is still necessary to reduce cost and enhance catalytic activity. Herein, we report an ultra-thin Ti 2 NT x MXene-wrapped metal-organic frameworks (MOFs)-derived CoP composite (Ti 2 NT x @MOF-CoP), which is a bifunctional catalyst with low cost and high activity. We synthesize the Ti 2 NT x @MOF-CoP composite by phosphating the precursor ZIF-67 self-assembled with Ti 2 NT x MXene nanosheets. The Ti 2 NT x @MOF-CoP electrode shows competitive hydrogen evolution performance in a wide pH-range (current density of 10 mA cm −2 ) and has a low overpotential ( η ) of 112 mV in pH = 14 especially. The Ti 2 NT x @MOF-CoP electrode for OER also has a low η  = 241 mV at 50 mA cm −2 . Based on the bifunctional activity of Ti 2 NT x @MOF-CoP in alkaline, we set a dual-electrode configuration for HER and OER. It has a bias of 1.61 V at 10 mA cm −2 , with impressive catalytic stability during a 20 h measurement. MOFs-derived CoP has a large specific surface area and strong catalytic activity. Ti 2 NT x as a novel member of the MXene family not only can increase the active sites, but also can improve the stability of heterojunction catalysts. It reveals that the Ti 2 NT x @MOF-CoP composite has great potential in hydrogen evolution and water oxidation, thus reducing carbon emissions and protecting the environment.

研究领域: 材料科学 · 能源化学
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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

Novel S-scheme WO3/RP composite with outstanding overall water splitting activity for H2 and O2 evolution under visible light

Shan Jiang,Jing Cao,Minna Guo,Dongdong Cao,Xuemei Jia,Haili Lin,Shifu Chen

Elemental red phosphorus (RP) has an ultra-low activity of splitting water for H 2 and O 2 evolution. In this study, RP was decorated by trace amount of WO 3 to greatly enhance the photocarriers separation and photocatalytic activity for overall water splitting under visible light. The 2.5% WO 3 /RP composite achieved the highest activity to produce H 2 and O 2 , and the activity was 7.0 times that of pure RP under visible light (λ ≥ 420 nm). The significantly increased photocarriers separation of WO 3 /RP was ensured by transient photocurrent, electrochemical impendence, photoluminescence, and time-resolved photoluminescence characterizations. More importantly, WO 3 /RP maintained high stability when it was persistently used for 20 cycles. Based on the reactive oxygen species ( O 2 − and OH) detected during the photocatalytic process, an S-scheme mechanism was proposed for WO 3 /RP composites to efficiently separate the photocarriers. This work provides a notion for improving the overall water splitting activity of RP via an S-scheme photocarriers separation mode.

研究领域: 材料科学 · 环境科学
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Nanoscale · 2020 ·Vol. 12 ·期 37 ·19404-19412 · IF 6.895

A multi-interfacial FeOOH@NiCo2O4 heterojunction as a highly efficient bifunctional electrocatalyst for overall water splitting

Xi Cao,Yan Sang,Lvxuan Wang,Gaofei Ding,Runhan Yu,Baoyou Geng

Electrocatalytic water decomposition is the key to sustainable energy, and the design and synthesis of cost-effective electrocatalysts is the main objective of electrocatalytic water splitting. In this paper, multi-interfacial FeOOH@NiCo2O4 hybrid nanoflowers are prepared through a two-step hydrothermal reaction. In such heterostructures, NiCo2O4 nanoflowers are coated with a layer of FeOOH nanoparticles. In addition, the obtained electrocatalyst could provide abundant electroactive sites and the formation of FeOOH@NiCo2O4 nanointerfaces can also improve the charge transfer rate. As a result, under the HER and OER conditions, the prepared catalysts show an outstanding electrocatalytic performance. Moreover, in a two-electrode water splitting system, the FeOOH@NiCo2O4 heterostructure, as a dual-function electrocatalyst, needs a cell voltage of only 1.58 V at a current density of 10 mA cm−2. This study provides a facile and feasible method to construct different kinds of heterostructures as bifunctional electrocatalysts with multiple interfaces by a simple hydrothermal method.

CAS / MDL: 7791-13-1 1310-58-3
研究领域: 材料科学 · 电化学
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