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MOLECULES · 2020 ·Vol. 25 ·期 9 ·2109 · IF 3.267

Photocatalytic Cleavage of β-O-4 Ether Bonds in Lignin over Ni/TiO2

Changzhou Chen,Peng Liu,Haihong Xia,Minghao Zhou,Jiaping Zhao,Brajendra K. Sharma,Jianchun Jiang

It is of great importance to explore the selective hydrogenolysis of β-O-4 linkages, which account for 45–60% of all linkages in native lignin, to produce valued-added chemicals and fuels from biomass employing UV light as catalyst. TiO2exhibited satisfactory catalytic performances in various photochemical reactions, due to its versatile advantages involving high catalytic activity, low cost and non-toxicity. In this work, 20 wt.% Ni/TiO2and oxidant PCC (Pyridinium chlorochromate) were employed to promote the cleavage of β-O-4 alcohol to obtain high value chemicals under UV irradiation at room temperature. The Ni/TiO2photocatalyst can be magnetically recovered and efficiently reused in the following four consecutive recycling tests in the cleavage of β-O-4 ether bond in lignin. Mechanism studies suggested that the oxidation of β-O-4 alcohol to β-O-4 ketone by oxidant PCC first occurred during the reaction, and was followed by the photocatalysis of the obtained β-O-4 ketone to corresponding acetophenone and phenol derivates. Furthermore, the system was tested on a variety of lignin model substrates containing β-O-4 linkage for the generation of fragmentation products in good to excellent results.Keywords:lignin;β-O-4;photocatalyst;Ni/TiO2;oxidant PCC

CAS / MDL: 13463-67-7 13478-00-7
研究领域: 化学工程 · 环境科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

Hydrodeoxygenation of Palmitic Acid with Novel Two-Dimensional Ti3C2Tx MXene-Supported Ni Catalyst

Junmei Liang,Qicheng Zhang,Haibo Zhao,Shaolei Zhao,Yulong Wu,Xiaobin Fan

Hydrodeoxygenation (HDO) of fatty acids to alkanes is key to convert renewable resources into biofuels. Here, we design a new Ti3C2Tx MXene-confined Ni catalyst with extraordinary catalytic performance in the HDO of palmitic acid. Due to the large two-dimensional surface and chemical activity, Ti3C2Tx MXene is able to disperse and anchor Ni particles through strong synergistic coupling. As a consequence, the obtained Ni/Ti3C2Tx catalyst exhibits excellent catalytic performance with a complete conversion of palmitic acid. It can be recycled in five runs without activity reduction, demonstrating good stability of the as-prepared catalyst. The facilitated catalytic performance can be ascribed to the synergic effect of metal Ni and Ti3C2Tx MXene. Ti3C2Tx MXene facilitates the adsorption and conversion of palmitic acid to aldehyde. The dispersed Ni particles benefit from the hydrogenation of hexadecanal intermediate with the cleavage of C–C bonds and the dehydration–hydrogenation of hexadecanol to form alkanes.

CAS / MDL: 7664-39-3
研究领域: 催化化学 · 可再生能源
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LANGMUIR · 2024 · IF 3.7

Photo-thermal Catalytic Hydrogenation of Halogenated Nitrobenzenes over Ni/P25 Catalyst

Jia-qi Bai,Jiahui Xu,Mei Ma,Zhengan Miao,Jiawen Yu,Huangfei Liu,Zhangkai Qian,Mengdie Cai,Qin Cheng,Yong Jiang,Song Sun

As haloanilines (HANs) are important organic intermediates and fine chemicals, their preparation over non-noble-metal-based catalysts by catalytic hydrogenation has attracted wide attention. However, the reaction suffers from relatively harsh conditions. Herein, we found that a 3.5%Ni/P25 catalyst exhibited superior photo-thermal catalytic activity with a TOFs of 5207 h–1 for hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline under a 300 W full spectrum, which was much higher than that of photo- and thermal catalysis alone. Moreover, the 3.5%Ni/P25 catalyst could be recycled 4 times and was effective for the hydrogenation of various halonitrobenzenes (HNBs) with superior selectivity. Furthermore, the kinetic research showed that the excellent catalytic performance could be attributed to the better activation and dissociation of H2 by photo-thermal catalysis and the hydrogenation of p-CNB obeyed the condensation routine by ionic hydrogenation over 3.5%Ni/P25.

研究领域: 化学工程 · 催化科学
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JOURNAL OF CATALYSIS · 2025 · IF 6.5

Promotional role of boron on Ni/SiO2 catalysts for dibenzofuran hydrodeoxygenation

Ting-Sheng Chen,Di Liu,Yun-Jie Li,Xing-Bao Wang,Chang-Hai Liang,Zhen-Yi Du,Wen-Ying Li

Controlling the oxygen-free product selectivity in catalytic hydrodeoxygenation is essential for producing high quality fuels from coal- and biomass-derived crude liquids. A series of boron-doped Ni/SiO 2 catalysts were prepared for the efficient hydrodeoxygenation of dibenzofuran as a model compound. Boron doping significantly promoted the transformation of 2-cyclohexylcyclohexanol, which was accumulated as the main oxygen-containing intermediate compound on the pristine Ni/SiO 2 catalyst, to the target products bicyclohexane and its isomer cyclopentylmethylcyclohexane. Characterization results show that boron doping increases Ni dispersion, modifies the electronic properties of Ni sites and in situ generates Brønsted acid sites by H 2 spillover to boron oxides. The reduced Ni particle size improves the rates of dibenzofuran hydrogenation and 2-cyclohexylcyclohexanol dehydration. Electron-deficient Ni and boron oxides as the Lewis acid sites enhance the adsorption of 2-cyclohexylcyclohexanol. Furthermore, the in situ generated Brønsted acid sites favor the dehydration of 2-cyclohexylcyclohexanol, which gives the Ni-5B/SiO 2 catalyst a better deoxygenation activity than the mechanical mixture of equal amounts of 5B/SiO 2 and Ni/SiO 2 , as well as the one with a smaller Ni particle size of 3.8 nm.

CAS / MDL: 13478-00-7 112945-52-5
研究领域: 催化化学 · 能源化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Integrated CO2 capture and In-Situ methanation by efficient dual functional Li4SiO4@Ni/CeO2

Zongze Lv,Jiaqi Ruan,Weifeng Tu,Xun Hu,Donglin He,Xin Huang,Changlei Qin

Integrated carbon capture and utilization by methanation (ICCU-methanation) is an emerging concept in reducing CO 2 emissions and storing H 2 simultaneously. One key of the technology is the development of dual functional materials (DFMs) that can efficiently capture CO 2 and then catalyze it. Herein, we propose the construction of DFM using Li 4 SiO 4 with superior CO 2 adsorption/desorption features as sorbent and catalyst carrier, CeO 2 as catalyst promoter and isolator, and Ni as catalytic metal, and comprehensively evaluate its characteristics and performance in ICCU-methanation. Results show that the DFM developed possess a high and stable CO 2 capacity of 5.4 mmol·g DFM -1 , 96 % CO 2 conversion and 96 % CH 4 selectivity under both the ideal CO 2 capturing atmosphere and the realistic flue gas containing 10 vol% steam and 8 vol% O 2 . Moreover, rapid CO 2 dissociation from the DFM is observed at a temperature lower to 560 °C due to the reaction of H* dissociated by catalyst with carbonate to form formate, which further decomposes to release CO.

研究领域: 能源化学 · 环境科学
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NANOTECHNOLOGY · 2023 ·Vol. 34 ·期 40 ·405201 · IF 3.5

Achieving high carrier separation over Bi4O5I2 through Ni doping for improved photocatalytic CO2 reduction

Zhuohua Chen,Xiaoli Jin,Qing Lan,Xin Li,Qunzeng Huang,Wenmin Liu,Yuwei Guo,Haiquan Xie,Liqun Ye

Photocatalytic CO2 reduction is considered to be an appealing way of alleviating environmental pollution and energy shortages simultaneously under mild condition. However, the activity is greatly limited by the poor separation of the photogenerated carriers. Ion doping is a feasible strategy to facilitate the charge transfer. In this work, Ni-doped Bi4O5I2 photocatalyst is successfully fabricated using a one-pot hydrothermal method. A few doping levels appear in the energy band of Bi4O5I2 after Ni doping, which are used as springboards for electrons transition, thus promoting photoexcited electrons and holes separation. As a consequence, a remarkably enhanced yield of CO and CH4 (6.2 and 1.9 μmol g−1 h−1) is obtained over the optimized Bi4O5I2-Ni15, which is approximately 2.1 and 3.8 times superior to pure Bi4O5I2, respectively. This work may serve as a model for the subsequent research of Bi-based photocatalysts to implement high-performance CO2 photoreduction.

研究领域: 材料科学 · 环境科学 · 能源科学
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MATERIALS & DESIGN · 2016 · IF 3.997

Synthesis and characterization of cross-like Ni-Co-P microcomposites

Yuhua Yan,Yanping Tian,Meifeng Hao,Yuqing Miao

The cross-like crystallines of Ni-Co-P microcomposites were synthesized via a simple hydrothermal method under high pressure and temperature which is adapted from the classical electroless deposition technique for surface modification. Here hypophosphite was employed as reductant and phosphorus resource to prepare the composites of Ni, Co and P elements. The obtain Ni-Co-P microcomposites were characterized in morphology, composition and properties. They show the perfect cross-like shape with an approximate stoichiometry of Ni 12 -Co 6 -P 12 -O 70 . The high absorbance in UV area and wide absorbance in vis area are observed. They also exhibit superparamagnetic behavior and hydrogen evolution property.

研究领域: 材料科学 · 化学
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RARE METALS · 2017 ·Vol. 37 ·期 2 ·148-153 · IF 1.189

Synthesis and properties of electrodeposited Ni–CeO2 nano-composite coatings

Jin Hui,Wang Yi-Yong,Wang Yu-Ting,Yang Hong-Bing

Current machinery requires metallic materials to have better surface properties. Based on an orthogonal experimental design and analysis method, the CeO 2 -reinforced nickel nano-composite coatings were prepared by direct current electrodeposition in a nickel sulfate bath containing CeO 2 nanoparticles. Statistical results indicate that current density is the most significant variable in the electrodeposition processing, while temperature is the least important factor. The microstructure of Ni and Ni–CeO 2 nano-composite coatings was characterized by scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The microhardness of the Ni coating is enhanced by the incorporation of CeO 2 nanoparticles. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to characterize the corrosion behavior of Ni and Ni–CeO 2 coatings. These studies show that Ni–CeO 2 coating has better corrosion resistance compared to Ni coating.

CAS / MDL: 1306-38-3
研究领域: 材料科学 · 电化学
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Journal of Materials Chemistry A · 2021 ·Vol. 9 ·期 10 ·6325-6334 · IF 12.732

Host dependent electrocatalytic hydrogen evolution of Ni/TiO2 composites

Peng Zhou,Shuhua Wang,Guangyao Zhai,Xingshuai Lv,Yuanyuan Liu,Zeyan Wang,Peng Wang,Zhaoke Zheng,Hefeng Cheng,Ying Dai,Baibiao Huang

Ni/TiO2 as a classic system has been widely studied in the traditional catalysis field including the water-gas shift reaction and selective oxidation/hydrogenation. However, in terms of the electrocatalytic hydrogen evolution reaction (HER), there is still a lack of systematic research on the actual synergistic promotion effect on the performance, and the influence of the host material on the electronic interaction between Ni and TiO2 is still unclear. Herein, we synthesized a series of Ni/TiO2 composites with different forms and tested the relevant HER performance. The results show that Ni/TiO2 exhibits much better HER performance than pure Ni and there is one type of electronic interaction between Ni and TiO2 in the composite with different forms, that is, electrons transfer from Ni to TiO2. However, the interaction strength is host dependent, and the composite with Ni as the host displays the strongest interaction, and therefore the best HER performance (46 mV at 10 mA cm−2).

研究领域: 材料科学 · 电化学
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Catalysis Science & Technology · 2019 ·Vol. 10 ·期 1 ·263-267 · IF 5.726

Facile synthesis of self-supported amorphous phosphorus-doped Ni(OH)2 composite anodes for efficient water oxidation

Gang Yuan,Yujie Hu,Zihan Wang,Qiwei Wang,Li Wang,Xiangwen Zhang,Qingfa Wang

Water oxidation plays a pivotal role in energy conversion and storage such as in water splitting and metal-air batteries. The development of a highly active and stable electrode for water oxidation at a low price is greatly challenging. Here, we report a self-supported oxygen evolution reaction (OER) electrode with a 3D porous Ni foam (NF) as a core and a dense layer of amorphous phosphorus-doped Ni hydroxide (Ni–OH/P) film as a shell. This facilely fabricated 3D core–shell structured electrode with directly grown active materials offered improved activity and prolonged stability for OER. It required an overpotential of 490 mV to deliver a current density of 100 mA cm−2; it showed a small Tafel slope at 87 mV dec−1 and sustained elongated electrolysis at 100 mA cm−2 for 100 h. The NiOOH shell was in situ formed on the surface of the Ni–OH/P film. Then, a new core–shell structured film was constructed. The synergetic effects of the newly formed crystalline NiOOH shell and amorphous Ni–OH/P core contributed to high stability under harsh conditions. This work presents a facile and easy scale-up path to develop self-supported hybrid electrodes for efficient and stable energy conversion and storage.

研究领域: 能源材料 · 电化学
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Catalysts · 2019 ·Vol. 9 ·期 6 ·538 · IF 3.444

Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde

Lili Liu,Xiaojing Zhou,Li Liu,Shuai Jiang,Yingjie Li,Luxia Guo,Shijuan Yan,Xishi Tai

Three bimetallic Cu–Ni nanoparticle-supported catalysts were synthesized by co-immobilization followed by H2reduction. A chromium(III) terephthalate metal organic framework (MIL-101), titanium dioxide (TiO2), and carbon (C) with different properties (acidity and Brunauer–Emmett–Teller surface area) were selected as supports for studying the effect of the support nature on the catalytic activity and selectivity in the oxidation of benzyl alcohol. The physicochemical properties of the Cu–Ni-supported catalysts were characterized by XRD, NH3-TPD, nitrogen adsorption/desorption, TEM, EDS, XPS, and ICP-OES. Bimetallic Cu–Ni nanoparticles were highly dispersed on the support. The catalytic activities of CuNi/MIL-101, CuNi/TiO2, and CuNi/C were tested in the selective oxidation of benzyl alcohol to benzaldehyde in the presence of molecular oxygen under mild reaction conditions. The highest benzaldehyde yields were achieved with CuNi/TiO2, CuNi/MIL-101, and CuNi/C catalysts at 100 °C within 4 h under 5, 3, and 3 bar of O2, respectively. The bimetallic Cu–Ni-supported catalysts possessed two types of catalytic active sites: acid sites and bimetallic Cu–Ni nanoparticles. The CuNi/MIL-101 catalyst possessed a high number of acid sites and exhibited high yield during selective benzyl alcohol oxidation to benzaldehyde. Importantly, the catalysts exhibited a high functional group (electron-donating and electron-withdrawing groups) tolerance. Cu–Ni-supported catalysts with an Cu:Ni mole ratio of 1:1 exhibited the highest yield of 47% for the selective oxidation of benzyl alcohol to benzaldehyde. Reusability and leaching experiment results exhibited that CuNi/MIL-101 showed better stability than CuNi/TiO2and CuNi/C catalysts due to the large porous cavities of MIL-101 support; these cavities can be used to trap bimetallic Cu–Ni nanoparticles and inhibit nanoparticle leaching.Keywords:Cu–Ni nanoparticles;MIL-101;TiO2;carbon;benzyl alcohol oxidation

研究领域: 催化 · 材料科学 · 化学工程
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ACS Catalysis · 2025 · IF 13.1

Efficient Cu–Ni/W20O58 Catalysts for Hydrogenation of Nitriles to Secondary Amines

Jia-qi Bai,Mei Ma,Huangfei Liu,Zhangkai Qian,Durui Liu,Yuncai Zhao,Yijing Gao,Jingshuai Chen,Mengdie Cai,Song Sun

The hydrogenation of nitriles is an environmentally friendly and atom-economical route to prepare high-value amines; however, it is still a challenge to control selectivity because of the occurrence of hydrogenation, self-coupling, and hydrogenolysis reactions during the hydrogenation process. It is highly desirable to develop efficient non-noble-metal catalysts for the hydrogenation of nitriles to secondary amines, although several noble metal catalysts have been reported. Herein, we successfully prepared a Cu–Ni/W20O58 catalyst and found that the Cu4.4–Ni0.6/W20O58 catalyst showed a 92.3% yield with initial TOFs of 270.0 h–1 at 373 K and 3 MPa H2 for the hydrogenation of benzonitrile (BN) to dibenzylamine (DBA), which was much superior to that of the monometallic Cu4.4/W20O58 and Ni0.6/W20O58 catalysts. Moreover, the Cu4.4–Ni0.6/W20O58 catalyst could be reused at least 4 times and was effective for the hydrogenation of various nitriles with superior selectivity to secondary amines. Furthermore, the reaction mechanism of BN hydrogenation for the Cu–Ni alloy of Cu4.4–Ni0.6/W20O58 was proposed on the basis of spectroscopic studies such as XRD, TPR, TEM, XAFS, and XPS, kinetic studies such as the effect of BN concentration and H2 pressure, the isotopic effect of hydrogen, and the effect of the reaction temperature and DFT calculations. The rate-determining step was the hydrogenation of benzylidenamine (BI) to the half-hydrogenated intermediate by one H atom over the Cu4.4–Ni0.6/W20O58 catalyst. The Ni–W20O58 interface was responsible for the adsorption and activation of BN, and the electron-rich Cu acted as the site for H2 dissociation; the synergistic effect of Cu and Ni led to the superior catalytic performance of the Cu4.4–Ni0.6/W20O58 catalyst.

研究领域: 催化化学 · 材料科学 · 环境化学
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