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Direct Synthesis of molybdenum phosphide Nanorods on Silicon Using Graphene at the Heterointerface for Efficient Photoelectrochemical Water Reduction

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Nano-Micro Letters 2021年第5期13卷 135-150页

作者： Sang Eon Jun Seokhoon Choi Shinyoung Choi Tae Hyung Lee Changyeon Kim Jin Wook Yang Woon‑Oh Choe In‑Hyuk Im Cheol‑Joo Kim Ho Won Jang Department of Materials Science and Engineering Research Institute of Advanced MaterialsSeoul National UniversitySeoul 08826Republic of Korea Department of Chemical Engineering Pohang University of Science and TechnologyPohang 37673Republic of Korea

Transition metal phosphides(TMPs)and transition metal dichalcogenides(TMDs)have been widely investigated as photoelectrochemical(PEC)catalysts for hydrogen evolution reaction(HER).Using high-temperature processes to get crystallized compounds with large-area uniformity,it is still challenging to directly synthesize these catalysts on silicon photocathodes due to chemical incompatibility at the ***,a graphene interlayer is applied between p-Si and MoP nanorods to enable fully engineered interfaces without forming a metallic secondary compound that absorbs a parasitic light and provides an inefficient electron path for hydrogen ***,the graphene facilitates the photogenerated electrons to rapidly transfer by creating Mo-O-C covalent bondings and energetically favorable band *** a bridging role of graphene,numerous active sites and anti-reflectance of MoP nanorods lead to significantly improved PEC-HER performance with a high photocurrent density of 21.8 mA cm−2 at 0 V versus RHE and high ***,low dependence on pH and temperature is observed with MoP nanorods incorporated photocathodes,which is desirable for practical use as a part of PEC *** results indicate that the direct synthesis of TMPs and TMDs enabled by graphene interlayer is a new promising way to fabricate Si-based photocathodes with high-quality interfaces and superior HER performance.

关键词： Photoelectrochemical water splitting Silicon molybdenum phosphide Hydrogen evolution Graphene

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Effect of Reduction Temperature on Hydrofining Performance of Supported molybdenum phosphide Catalyst

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Journal of Natural Gas Chemistry 2005年第4期14卷 233-237页

作者： Fengyan Li Zhifang Zhao Qingjie Li Tianbo Zhao Cuiqing Li Guida Sun Department of Applied Chemistry Beijing Institute of Petrochemical Technology Beijing 102617 China School of Science Beijing Institute of Technology Beijing 100081 China

A series of supported molybdenum phosphide catalysts were prepared by impregnation method. XRD, TG-DTG, XPS and BET were used to study the phase, compositions and surface areas of the prepared catalysts. A model reactant containing thiophene, pyridine and cyclohexene was used for the measurements of catalytic activities. The effect of reduction temperature on catalytic activities was investigated. The analysis results by XRD and BET are very different when the reduction temperature is changed from 400 to 900 ℃. MoP/γ-Al2O3 catalysts and CoMoP/γ-Al2O3 catalysts prepared at the reduction temperature of 500 ℃ are the most active ones.

关键词： molybdenum phosphide reduction temperature hydrodenitrogenation hydrodesulfurization supported catalyst

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Phytic acid-derived fabrication of ultra-small MoP nanoparticles for efficient CO methanation: Effects of P/Mo ratios

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Journal of Energy Chemistry 2020年第8期29卷 248-255,I0009页

作者： Jun Zhao Zijia Yin Baowei Wang Zhenhua Li Yan Xu Xinbin Ma Key Laboratory for Green Chemical Technology of the Ministry of Education School of Chemical Engineering and TechnologyTianjin UniversityTianjin 300072China

molybdenum phosphide(MoP) catalyst has been widely applied in hydrogenation reactions, while the preparation of unsupported MoP catalysts with ultra-small size and large specific surface area(SBET) is still challenging. Herein, we have provided a facile method for preparing a series of MoP-x(x=P/Mo ratios ranging from 1 to 5) catalysts by pyrolyzing phytic acid(PA)-derived Mo complexes in a H2 atmosphere. The physicochemical properties and the catalytic activity of MoP catalysts were investigated. The results showed that the obtained MoP-5 catalyst had the largest SBETand exhibited ultra-small nanoparticle diameter of 3.6 nm, which ascribed to the chelation of PA and the confinement of deposited *** the content of PA increased, the synthetic mechanism of MoP was also affected, which led to the difference in the valence of surface Mo species. The characterization results further confirmed that Moδ+ sites in MoP catalysts are active sites for methanation reaction and its content on the surface of MoP-x catalysts determines the catalytic activity.

关键词： molybdenum phosphide Phytic acid P/Mo ratios Ultra-small nanoparticle CO methanation

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MoP nanoparticles with a P-rich outermost atomic layer embedded in N-doped porous carbon nanofibers： Self-supported electrodes for efficient hydrogen generation

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Nano Research 2018年第9期11卷 4728-4734页

作者： Minqiang Wang Cui Ye Maowen Xu Shujuan Bao Institute for Clean Energy & Advanced Materials Faculty of Materials and Energy Southwest University Chongqing 400715 China Key Laboratory of Eco-Environments in Three Gorges Reservoir Region (Ministry of Education) School of Chemistry and Chemical Engineering Southwest University Chongqing 400715 China

Despite being pursued for a long time, hydrogen production via water splitting is still a huge challenge mainly due to a lack of durable and efficient catalysts. molybdenum phosphide （MOP） is theoretically capable of efficient hydrogen evolution reaction （HER） catalysis, however, there is still room for further improvement in its performance. Herein, we propose a design for MoP with a P-rich outermost atomic layer for enhancing HER via complementary theoretical and experimental validation. The correlation of computational results suggests that the P-terminated surface of MoP plays a crucial role in determining its high-efficiency catalytic properties. We fabricated a P-rich outermost atomic layer of MoP nanoparticles by using N-doped porous carbon （MoP@NPCNFs） to capture more P on the surface of MoP and limit the growth of nanoparticles. Further, the as-prepared material can be directly employed as a self-supported electrocatalyst, and it exhibits remarkable electrocatalytic activity for HER in acidic media; it also reveals excellent long-term durability for up to 5,000 cycles with negligible loss of catalytic activity.

关键词： P-rich outermost atomiclayer molybdenum phosphide density function theor^self-supported electrocatalyst hydrogen evolution reaction

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