Collection of Energy Materials 4(2020)

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Research Progress of Novel Two-dimensional Materials in Photocatalysis and Electrocatalysis
LI Neng,KONG Zhouzhou,CHEN Xingzhu,YANG Yufei
Journal of Inorganic Materials    2020, 35 (7): 735-747.   DOI: 10.15541/jim20190388
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Two-dimensional materials have attracted broad interest because of their wide variety of properties. They can be used as photocatalysts and electrocatalysts due to their extremely high specific surface area, and have great potential application in the field of environment and renewable energy. This review focuses on the structure and properties of common two-dimensional materials such as 2D carbides and nitrides (MXenes), g-C3N4 and black phosphorus (BP). Furthermore, the latest research on the modification of two-dimensional materials in the area of photocatalysis and electrocatalysis are discussed and commented. Finally, research prospects for two-dimensional materials in the future are predicted.

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Cited: CSCD(3)
Synergistic Effect of Ag and Ag2O on Photocatalytic H2-evolution Performance of TiO2
WANG Ping,LI Xinyu,SHI Zhanling,LI Haitao
Journal of Inorganic Materials    2020, 35 (7): 781-788.   DOI: 10.15541/jim20190460
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Highly efficient TiO2 photocatalysts (TiO2/Ag-Ag2O) co-modified by Ag as electron cocatalysts and Ag2O as interfacial catalytic active sites were synthesized via a two-step process including the initial photoinduced deposition of metallic Ag nanoparticles on the TiO2 surface (TiO2/Ag) and the following in situ oxidation of partial Ag into Ag2O by low-temperature calcination. Ag nanoparticles function as effective electron cocatalysts for the steady capture and rapid transportation of photogenerated electrons from TiO2 surface to Ag2O, while the adsorbed H+ ions from solution to Ag2O as the interfacial catalytic active sites are reduced into H2. The synergistic effect of Ag and Ag2O can accelerate the electrons transfer and promote the rapid H2-evolution reaction for enhanced photocatalytic H2-evolution performance of TiO2/Ag-Ag2O. The highest H2-evolution rate of the resultant TiO2/Ag-Ag2O calcinated at 300 ℃ reached 75.20 μmol/h, which was higher than those of the TiO2 (3.59 μmol/h) and TiO2/Ag (41.13 μmol/h) by 21.0 and 1.8 times, respectively. This study provides a new strategy for the design and synthesis of highly efficient photocatalytic H2-evolution materials.

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Cited: CSCD(1)
Hydrothermal Synthesized Nickel Copper Composite Phosphides as Bifunctional Electrocatalysts for Hydrogen Evolution and Hydrazine Oxidation
LI Zhao, SUN Qiangqiang, CHEN Suoqian, ZHOU Chunsheng, CAO Jing, WANG Yongfeng, WANG Yanan
Journal of Inorganic Materials    2020, 35 (10): 1149-1156.   DOI: 10.15541/jim20190640
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Herein, we report a kind of NiCu-based composite phosphides electrocatalyst(NiCuP/NM), which was prepared in situ on nickel mesh substrate by one-step hydrothermal method with NaH2PO2, CuSO4, NiSO4 as initial materials. The morphology, crystal structure, composition, and electrocatalytic performance of NiCuP/NM were characterized. Under the optimal preparation conditions of Ni, Cu and P(molar ratio 8 : 1 : 20), hydrothermal synthesis at 140 ℃ for 24 h, the obtained composite electrocatalyst displayed three-level micro-nanostructure with Ni2P and Cu3P as main crystal phases. At the current density of 10 mA·cm -2, the required HER (Hydrogen Evolution Reaction) overpotential and HzOR (Hydrazine Oxidation Reaction) potential of NiCuP/NM were 165 and 49 mV, respectively. In the two-electrode system, the decomposition tank pressure for the NiCuP/NM cell at the same current density was only 0.750 V which remained substantially unchanged for 24 h catalysis, exhibiting excellent catalytic stability. NiCuP/NM displays prominent electrocatalytic performances towards HER or HzOR in both three-electrode and two-electrode systems, which can be ascribed to two aspects. On the one hand, the 14-fold electrochemical active surface area compared with original nickel mesh enables NiCuP/NM expose huge number of catalytic active sites in both HER and HzOR. On the other hand, the electronic structure modification of Ni and Cu atoms induced by doping P atom brings great improvement of intrinsic HzOR activity of electrode materials. This study provides a new perspective for nanoscale synthesis and promotes the development of novel nanopores in fuel cell and energy conversion applications.

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Cited: CSCD(1)
Durability of Fe-N/C Catalysts with Different Nanostructures for Electrochemical Oxygen Reduction in Alkaline Solution
DING Sheng, NING Kai, YUAN Binxia, PAN Weiguo, YIN Shibin, LIU Jianfeng
Journal of Inorganic Materials    2020, 35 (8): 953-958.   DOI: 10.15541/jim20190547
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The mechanism of Fe-N/C catalysts in oxygen reduction reactions is critical to the development of efficient, sustainable non-noble metal catalysts in polymer electrolyte membrane fuel cells, but it is still in controversy. In order to understand the relationship between composition and the nanostructure of material and the electrochemical activity, this study developed a type of Fe-N/C catalyst with high electrochemical activity, which contained Fe-Nx active sites and Fe/Fe3C nanocrystals encapsulated with nitrogen-doped carbon nanotubes. Despite being free of precious metals, the as-prepared catalyst displays high oxygen reduction reactions (ORR) activity in alkaline medium with the half-wave potential of 0.86 V(vs RHE), the mass activity of 18.84 A/g at 0.77 V(vs RHE), and the maximum current density of -4.3 mA·cm -2. Meanwhile, the electron transfer number is 3.7 at 0.2 V(vs RHE), revealing that the 4-electron ORR reaction exists in the catalyst. The excellent electrochemical activity is attributed to the graphene-encapsulated metallic Fe/Fe3C nanocrystals which improves the conductivity after the growth of N-doped carbon nanotubes, and the relatively high proportion of Fe-Nx active sites distributed on the surface of Fe/Fe3C nanoparticles. This study provides a certain reference and basis for the further study of non-noble metal catalyst and their wide application in commercial production.

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Cited: CSCD(1)
Preparation and Photoelectrochemical Property of the Dual-ferroelectric Composited Material
ZHANG Yaping,LEI Yuxuan,DING Wenming,YU Lianqing,ZHU Shuaifei
Journal of Inorganic Materials    2020, 35 (9): 987-992.   DOI: 10.15541/jim20190516
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BiVO4 film was synthesized via template method, the ferroelectric material BiFeO3 was prepared by Sol-Gel method to modify BiVO4. By means of dual-ferroelectric semiconductor composition, the photochemical properties of BiVO4 was greatly improved. The electrochemical test results show that the superior photoelectrochemical properties of BiVO4 film are achieved after spin-coating with BiFeO3 for 5 times. It owns an optimal photocurrent density of 0.72 mA·cm-2, which is 67.4% higher than that of pure BiVO4. The energy band bending regulation via electric field polarization could further boost the photoelectrochemical property of BiVO4/nBiFeO3 ferroelectric composite. The highest photocurrent density of the composite after polarization at 20 V reaches 0.91 mA·cm-2, which is more than twice of pure BiVO4 film. The combination of BiFeO3 and BiVO4 is favorable for forming heterojuncting, generating and separating of photogenic electrons and holes. The electric field polarization regulating band bending accelerates the photogenic charge transfer, which is the main reason for the improved photoelectrochemical properties of ferroelectric composite.

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Lattice Control of WO3 Nanoflowers by Heat Treatment and Construction of WO3/CdS/α-S Heterojuntion
LIN hai, SU Weitao, ZHU Yu, PENG Pai, FENG Miao, YU Yan
Journal of Inorganic Materials    2020, 35 (12): 1349-1356.   DOI: 10.15541/jim20200023
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In order to study the influence mechanism of heat treatment and heterostructures on the photoelectrochemical effect of WO3, monoclinic WO3 nanoflowers were synthesized by low-temperature solvothermal method. The active crystal fact, grain size and crystallinity of WO3 were controlled by heat treatment. Furthermore, WO3/CdS/α-S heterojunction was obtained by modified chemical bath deposition, and the concentration effect of its photoelectrochemical performance was studied. The results show that the (200) crystal plane with photoelectrochemical activity is the main exposed crystal plane of WO3, and the proportion of the exposed crystal plane increases with the heat treatment temperature increasing. The WO3 nanoflower treated at 350 ℃ showed the highest photoresponse current. By constructing WO3/CdS/α-S heterojunction, the material's absorption in the visible light region is enhanced, and the overall efficiency of photo-generated carrier separation is improved by sacrificing a small amount of carriers, which promotes the macroelectronic chemical effects of WO3.

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RuFe Nanoparticles Modified Sheet-like BiVO4 : High-efficient Synergistic Catalyst for Ammonia Borane Hydrolytic Dehydrogenation
ZHANG Yiqing,ZHANG Shujuan,WAN Zhengrui,MO Han,WANG Niangui,ZHOU Liqun
Journal of Inorganic Materials    2020, 35 (7): 809-816.   DOI: 10.15541/jim20190502
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Developing highly efficient and low-cost catalysts is crucial in the field of clean energy economy, in which ammonia borane (AB) has attracted great attention due to its high hydrogen production through the catalytic hydrolysis. In this work, BiVO4 nanosheet was firstly synthesized by a facile reflux method. And then bimetallic RuFe@BiVO4 catalysts with different molar ratios of Ru/Fe were prepared via in situ impregnation-reduction techniques and their catalytic activities were also tested in the hydrogen generation from aqueous solution of AB at room temperature. Compared with the releasing hydrogen rates of catalysts of BiVO4, Ru@BiVO4, Fe@BiVO4, RuFe NPs and RuFe@BiVO4, respectively, Ru1Fe0.1@BiVO4 exhibits the highest catalytic activity for the dehydrogenation of AB among all catalysts, the activation energy (Ea) and turnover frequency (TOF) are 43.7 kJ·mol-1 and 205.4 molH2·molRu·min-1, respectively. The addition of non-noble Fe can significantly enhance the catalytic activity of Ru counterparts, which is closely related to the strong electronic effect between Ru and Fe NPs, bi-functional effect generated between the RuFe NPs and the support BiVO4.

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