APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Wei Lin,Yuexing Zhang,Zixu Ma,Zhiwei Sun,Xiaolong Liu,Chunbao Charles Xu,Renfeng Nie
Selectivity controlling is a crucial and challenging issue for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). Herein, Ni 3 Sn 2 -ReO x /TiO 2 is synthesized via successive impregnation and exhibits full conversion and 92.5 % CPO selectivity under 3.0 MPa H 2 at 140 °C, which are much higher than those of Ni/TiO 2 and Ni 3 Sn 2 /TiO 2 . Characterizations show that Ni 3 Sn 2 is the main active phase that remarkably restrains the over-hydrogenation of the furan ring, while ReO x plays an electrophile or Lewis acid site to activate C-OH of furfuryl alcohol and induces its rearrangement. DFT calculations verify that Sn doping weakens the furan ring adsorption on Ni 3 Sn 2 and shifts its adsorption configuration, which consequently inhibits side reactions and favors the metal-acid (Ni 3 Sn 2 -ReO x ) synergy. The catalyst is stable, recyclable and also active at even 0.5 MPa H 2 and 80 °C. This study provides an advanced strategy for the rational design of superior catalysts for tuning product selectivity, with practical potential for upgrading biomass-derived platform molecules.
研究领域:
催化化学
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生物质转化
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理论计算
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产品关联
DOI
高影响因子
Catalysis Science & Technology
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2021
·Vol. 11
·期 15
·5125-5134
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IF 6.119
Yanke Yu,Xianfang Yi,Jiali Zhang,Zhaojian Tong,Changwei Chen,Mudi Ma,Chi He,Jinxiu Wang,Jinsheng Chen,Bingbing Chen
Non-vanadium-based catalysts with high SO2 tolerance are still interesting in selective catalytic reduction of NO by NH3 (NH3-SCR) and SO2 adsorption is the foremost step for the deactivation of catalysts. In order to alleviate the adsorption of SO2, we fabricated a series of rhenium (Re; without stable sulfate) supported TiO2 catalysts and studied their SO2 tolerance for the first time. Owing to suitable surface acidity and reducibility, ReOx/TiO2 catalysts exhibited satisfactory activity in a wide temperature range of 250–350 °C. As expected, experimental results and DFT calculations indicated that SO2 adsorption on ReOx/TiO2 catalysts was rather weak, thus the catalysts performed excellent SO2 tolerance in the NH3-SCR reaction. Moreover, in situ DRIFTS indicated that the NH3-SCR reaction on ReOx/TiO2 catalysts followed the Eley–Rideal mechanism and SO2 had little effect on the reaction mechanism. Our findings should provide new insights into the development of SCR catalysts with high SO2 tolerance.
研究领域:
催化化学
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环境科学
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产品关联
DOI
高影响因子
ACS Catalysis
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2023
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IF 12.9
Wei Lin,Yi Chen,Yuexing Zhang,Yongsheng Zhang,Jianshe Wang,Liucheng Wang,Chunbao Charles Xu,Renfeng Nie
Ni–ReOx bimetallic catalysts (Ni–ReOx/TiO2) were prepared through a successive impregnation method, which is extremely active in furfural (FAL) hydrogenation to tetrahydrofurfuryl alcohol (THFOL) under mild reaction conditions. For instance, high FAL initial reaction rate (439.4 mmol/g-Ni/h) and THFOL formation rate (80.4 mmol/g-Ni/h) were achieved over Ni–5ReOx/TiO2, which are 13.2 and 6.6 times higher than those of Ni/TiO2, respectively. The unique catalyst reactivity derives from rich Lewis acidic ReOx and intimate electron interaction of ReOx with Ni NPs. Kinetic studies reveal that ReOx decoration decreases the activation barrier of −C═O hydrogenation other than the furan ring. Mechanism studies show that ReOx has a good affinity for C═O and H2 and favors hydrogen spillover and C═O bond activation on Ni, thus reinforcing the synergistic effect of Ni and ReOx. This catalyst is versatile for various furan aldehydes and is relatively stable for 5 times recycling, showing relative potential for industrial application.
研究领域:
催化化学
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能源化学
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材料科学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2022
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IF 12.92
Guang Gao,Zelun Zhao,Jia Wang,Yongjie Xi,Peng Sun,Fuwei Li
ABSTRACT Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide (MO x ) or support has been a common method for improving the catalytic performance of supported metal catalysts. However, few studies have investigated the ternary interactions among the metal, MO x , and support. Here, we report for the first time the formation of metal-MO x -support interaction (MMSI) in reducible TiO 2 -supported PtReO x catalysts, affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol; the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents. Detailed experimental and computational studies suggest that the TiO 2 crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReO x -TiO 2 interactions, which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate, thus promoting the hydrogenation activity and selectivity. In addition, the strong MMSI endows the optimal rutile TiO 2 supported PtReO x catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids. This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C–O and C=O bonds.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Yanke Yu,Desheng Wei,Zhaojian Tong,Jinxiu Wang,Jinsheng Chen,Chi He
Ammonia (NH 3 ) is a critical component causing environmental problems like haze and water pollution. Selective catalytic oxidation of ammonia (NH 3 -SCO) to N 2 and H 2 O is a promising method to abate NH 3 emission. However, inferior SO 2 tolerance is still a tremendous challenge to be conquered for present NH 3 -SCO catalysts regarding practical applications. Application of materials which was difficult to be sulfated by SO 2 should be an effective way to solve this problem. Here, a ReO x -CuSO 4 /TiO 2 catalyst which coupled the advantages of ReO x (Rhenium oxides, supplying highly active adsorbed surface oxygen enhancing NH 3 -SCO reaction) and CuSO 4 (providing Brønsted acid sites inhibiting the formation of N 2 O) was rationally fabricated. Results indicated that ReO x -CuSO 4 /TiO 2 catalyst exhibited excellent catalytic performance in NH 3 -SCO with almost 100% of NH 3 oxidized at 300 °C (N 2 selectivity as high as 96%). Crucially, the composite catalyst exhibited incredible activity and stability under harsh reaction conditions toward SO 2 (600 ppm) and H 2 O (4.0 vol%) owing to the superior inhibition capability for SO 2 adsorption. In situ DRIFTS, in situ Raman and in situ XPS demonstrated that the NH 3 -SCO reaction over ReO x -CuSO 4 /TiO 2 catalyst mainly obeyed a N 2 H 4 reaction mechanism and oxidation–reduction circle between Re 7+ and Re 6+ played a vital role. Moreover, SO 2 would not affect this reaction mechanism on ReO x -CuSO 4 /TiO 2 catalyst. The knowledge and understanding reported could provide critical insights for the design and optimization of efficient materials for industrial NH 3 oxidative elimination.
研究领域:
催化化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
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2023
·Vol. 11
·期 36
·19591-19604
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IF 11.9
Feng Long,Yuwei Chen,Haitian Chen,Xincheng Cao,Shiyu Wu,Yanju Lu,Peng Liu,Jianchun Jiang,Xiaolei Zhang,Junming Xu
Enhancing both the reactivity and stability of catalysts for the hydrogenation of bio-derived fatty acids is a formidable challenge. In this study, we developed a Ni-ReOx/TiO2 catalyst, featuring Ni metal clusters encapsulated by ReOx active sites anchored on the TiO2 surface, for the hydrogenation of bio-derived fatty acids. Remarkably, the Ni-ReOx/TiO2 catalyst with a relatively low Re loading (approximately 4.4 wt%) exhibited outstanding performance in fatty alcohol production at a reduced temperature of 165 °C (yield: 95.3%) and alkane production at 205 °C (yield: 100.0%), outperforming the Cu-ReOx/TiO2 catalyst. Density functional theory (DFT) calculations unveiled that the introduction of ReOx onto the anatase surface led to modifications in electronic distribution and enhanced the interaction between the support and the metal. By integrating the DFT calculations with experimental results, we elucidated the roles played by the Ni clusters and Re–O active sites in the Ni-ReOx/TiO2 catalyst: facilitating H2 dissociation, promoting acid adsorption, and ultimately contributing to acid hydrogenation conversion. The industrial-scale processes for alkane and alcohol production were designed and simulated using Aspen Plus, enabling a quantitative assessment of the remarkable reaction activity of the Ni-ReOx/P25 catalyst. Additionally, the Ni-ReOx/P25 catalyst demonstrated excellent stability over four recycling cycles, coupled with robust water tolerance, thus showcasing its immense potential for application in industrial fuel and fatty alcohol production.
研究领域:
催化
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化学工程
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材料科学
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计算化学
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DOI
高影响因子
FUEL
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2024
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IF 6.7
Leilei Zhou,Liyan Zhang,Jingrong Li,Tingting Xiao,Peikai Luo,Xinluona Su,Haiyang Cheng,Fengyu Zhao
The hydrodeoxygenation of fatty acids and esters is a critical pathway to produce biofuels. We report an efficient RuRe/ZSM-5(18) catalyst for hydrodeoxygenation of methyl laurate, the selectivity of n -C 12 H 26 reached up to 95.2 % at complete conversion under the reaction conditions of 200 °C, 3 MPa H 2 , 3 h. The contribution of ReO x and acid sites was discussed from the perspective of dynamics and thermodynamics. ReO x was available for the adsorption of substrate and intermediates, the acidity from ReO x species and ZSM-5 are conducive to the cleavage of C O bond. The synergistic effects of ReO x and Brønsted acid sites induced Ru 0 species to be electron-deficient, which preferred to adsorb aldehyde group in a linear adsorption configuration and facilitated for the hydrogenation of the aldehyde intermediate to alcohol, followed by dehydration to produce hydrocarbons. Thus, RuRe/ZSM-5(18) catalyst presented superior activity and chemoselectivity in the hydrodeoxygenation of methyl laurate as well as a series of fatty acids and esters without loss in carbon numbers in reactant.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
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2024
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IF 9.3
Binbin Zhou,Nan Wang,Sibao Liu,Guozhu Liu
Renewable lubricant base oils derived from biomass can effectively mitigate environmental challenges while exhibiting exceptional properties. Herein, we propose a novel approach for the synthesis of ester-based and alkane-based renewable lubricant base oils, achieving an impressive yield of up to 99%. This strategy involves the utilization of methyl oleate and biomass-derived aromatics through two distinct chemistries: alkylation and alkylation followed by hydrodeoxygenation (HDO). Among the various Lewis acid catalysts screened, AlCl3 demonstrated superior performance and achieved a remarkable maximum yield of 99% for the alkylation product under the optimized reaction conditions. Subsequent hydrodeoxygenation (HDO) of these alkylation products using the Ir-ReOx/SiO2 catalyst resulted in the production of alkane-based lubricant base oils, with an impressive maximum yield of 96.3%. The molecular size and branching of ester-based and alkane-based products can be finely adjusted by employing diverse aromatic compounds during the alkylation process, thereby enabling tuning of their lubricant properties. The as-synthesized base oils exhibit superior properties to petroleum-derived group III base oils and demonstrate comparable performance to synthetic ester and PAO base oils. The presented strategy for synthesizing renewable base oils offers a sustainable alternative to petroleum-derived counterparts, thereby potentially mitigating greenhouse gas emissions.
研究领域:
化学工程
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可持续化学
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材料科学
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环境科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）