ACS Sustainable Chemistry & Engineering
·
2022
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IF 9.224
Yang Zeng,Lan Jiang,Xiaoxin Zhang,Songhai Xie,Yan Pei,Gongbing Zhou,Weiming Hua,Minghua Qiao,Zhen-Hua Li,Baoning Zong
Catalytic hydrogenolysis of biomass-derived glycerol to 1,3-propanediol (1,3-PDO) represents an important process for the sustainable production of value-added chemicals. However, there is a dearth of understanding of the effect of the polymorph of the support on this reaction. Herein, two Pt–WOx/TiO2 catalysts supported on rutile TiO2 (r-TiO2) and anatase TiO2 (a-TiO2) polymorphs were prepared to investigate the crystal phase effect of TiO2 on the structural property and catalytic performance in glycerol hydrogenolysis. The TiO2 polymorph was identified to impose profound effects on the size of the Pt nanoparticles (NPs) and the dispersion and location of the WOx species, which originated from the discrepancies in the crystal structures between the PtO2 and the TiO2 polymorphs and the discrepancies in the interactions of WOx with different TiO2 polymorphs. In glycerol hydrogenolysis, the Pt–WOx/r-TiO2 catalyst gave a 1,3-PDO selectivity of 51.2% at a glycerol conversion to liquid products of 74.5%, yielding 38.1% of 1,3-PDO. In contrast, the Pt–WOx/a-TiO2 catalyst showed much inferior glycerol conversion and 1,3-PDO selectivity, yielding only 1.0% of 1,3-PDO under identical reaction conditions. The superior catalytic performance of the Pt–WOx/r-TiO2 catalyst is attributed to the r-TiO2 polymorph that facilitates a faster hydrogen spillover than the a-TiO2 polymorph from the Pt NPs to the reaction intermediate on the WOx species, which is substantiated by an even higher 1,3-PDO yield of 44.8% over the physically mixed Pt/r-TiO2 + WOx/r-TiO2 catalyst. This work demonstrates the critical role of the polymorph of the TiO2 support in the design of efficacious Pt–WOx-based catalysts for glycerol hydrogenolysis to 1,3-PDO.
研究领域:
催化化学
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材料科学
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可再生能源
✓ 已验证
DOI
高影响因子
Journal of Physical Chemistry C
·
2021
·
IF 4.126
Qianghua Xin,Shitao Yu,Long Jiang,Defu Yin,Lu Li,Congxia Xie,Qiong Wu,Hailong Yu,Yuxiang Liu,Yue Liu,Shiwei Liu
The preparation of small molecule compounds with a high value from biomass has always been the focus of research, and catalysts with high activity and stability are an essential part of biomass conversion. In this work, yolk–shell nanospheres (YSNSs) with the high hydrogenation activity metal Pd as the core and mesoporous silica as the shell were prepared firstly, and then the bifunctional catalyst Pd@WOx–MSiO2 YSNSs was obtained by loading tungsten oxide on the surface of yolk–shell nanospheres. The structure characterization showed that the prepared Pd@WOx–MSiO2 YSNSs had a good shell–void–core structure, the amorphous WOx species was uniformly dispersed on the surface and channel of the mesoporous silica shell, and there were no bulky WO3 crystals. A series of Pd@WOx–MSiO2 YSNSs catalysts with different tungsten contents were used to catalyze the directional preparation of ethylene glycol (EG) from glucose. The conversion of glucose was 99.3% and the selectivity of EG was 59.4%. According to the analysis of the acidity of the catalyst and the valence state of the metal, the catalyst had weak Lewis acidity, which could promote the cleavage of the C–C bond in glucose, and W5+ could produce oxygen vacancy to adsorb oxygen into glucose, so that the tungsten species can effectively promote the selectivity of EG. Pd@WOx–MSiO2 YSNSs were very different from other supported catalysts in structure and the distribution of active sites. Compared with traditional supported catalysts, Pd@WOx–MSiO2 YSNSs had higher activity and stability due to their unique yolk–shell structures and the protection of the inner Pd nanoparticles by the mesoporous silica shell.
研究领域:
催化
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材料科学
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化学工程
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生物化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Mingxin Lv,Qianghua Xin,Defu Yin,Zhen Jia,Chunyan Yu,Teng Wang,Shitao Yu,Shiwei Liu,Lu Li,Yue Liu
The use of cellulose instead of oil to produce 1,2-propylene glycol (1,2-PG) is of great significance for building a sustainable world. Herein, we synthesize Fe3O4@SiO2/Ru-WOx core–shell magnetically recoverable catalysts containing both Lewis acid and metal active sites using well-shaped Fe3O4@SiO2 core–shell magnetic nanospheres as the substrate. We investigated the catalytic performances of the bimetallic catalysts with various metals as well as different metal contents and WOx loadings for the conversion of cellulose to 1,2-PG. The results showed that Fe3O4@SiO2/10%Ru-20%WOx was more favorable for 1,2-PG production, with a 1,2-PG selectivity of 32.4% and a cellulose conversion of 96.8%. Our characterization and activity tests suggested that WOx on the Fe3O4@SiO2 nanospheres produced abundant Lewis acid sites to effectively promote glucose isomerization to fructose before glucose undergoes the retro-aldol condensation reaction. Moreover, the Ru further hydrogenated the C3 intermediate to 1,2-PG. It was notable that the catalyst can be separated through a simple magnetic separation after the end of the reaction, and it still maintained high catalytic activity after 5 uses.
研究领域:
化学工程
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催化
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可持续化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2021
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IF 9.229
Shan Ni,Hongnan Qu,Huifang Xing,Zihao Xu,Xiangyang Zhu,Menglei Yuan,Li Wang,Jiemiao Yu,Yanqing Li,Liangrong Yang,Huizhou Liu
Exploiting precious-metal-free and high-activity oxygen evolution reaction (OER) electrocatalysts has been in great demands toward many energy storage and conversion processes, for example, carbon dioxide reduction, metal–air batteries, and water splitting. In this study, the simple solid-state method is employed for coupling Ni (electron donors) with lower-Fermi-level MoO2 or WOx (electron acceptors) into donor–acceptor ensembles with well-designed interfaces as robust electrocatalysts for OER. The resulting Ni/MoO2 and Ni/WOx electrocatalysts exhibit smaller overpotentials of 287 and 333 mV at 10 mA cm–2 as well as smaller Tafel slopes of 51 and 65 mV/dec, respectively, with respect to the single Ni, MoO2, WOx, and even the benchmark RuO2 in 1 M KOH. Specially, on account of a higher Fermi level of Ni in comparison with MoO2 and WOx, their strong electronic interaction results in directional interfacial electron transfer and increases the hole density over Ni, dramatically enriching the population of high-valence Ni3+ active sites and decreasing the Fermi level of Ni. The existence of Ni3+ can strengthen the chemisorption of OH–, and the downshift of the Ni Fermi level can significantly expedite migration of electrons toward the surface of catalysts during OER, thus synergistically boosting the OER catalytic performance. Furthermore, the inner Ni/MoO2 and Ni/WOx heterostructures and the electrochemically induced surface layers of oxides/hydroxides collectively boost the OER kinetics. This study highlights the importance of designing highly efficient OER electrocatalysts with high-valence active species (Ni3+) and better matched energy levels induced by the work function difference through interfacial engineering.
研究领域:
电化学
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材料科学
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能量存储与转换
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产品关联
DOI
PubMed
高影响因子
CELLULOSE
·
2020
·Vol. 27
·期 13
·7591-7605
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IF 4.21
Wang Haiyong,Hu Xiaohong,Liu Siwei,Cai Chiliu,Zhu Changhui,Xin Haosheng,Xiu Zhongxun,Wang Chenguang,Liu Qiying,Zhang Qi,Zhang Xinghua,Ma Longlong
The bi-functional Ni–W@C catalysts were prepared by one-pot reduction–carbonization method and used in hydrogenolysis of cellulose as well as raw lignocellulosic biomass to chemicals. The catalytic performance for cellulose conversion showed that it was more favorable for ethylene glycol (EG) production, obtaining the highest EG yield 60.1% over the Ni–W@C 700 catalyst. The Ni–W@C bimetallic catalysts are systematically characterized with BET, XRD, Raman, XPS, TEM techniques and experiments to probe the active catalytic sites of the catalysts. The effects of calcination temperature of Ni–W catalysts, reaction time, temperature and H 2 pressure on cellulose hydrogenolysis were investigated in detail. The Ni particles could lead to produce more W 5+ active sites, which promotes the glucose retro-aldol condensation to break the target C–C bonds. Metallic Ni catalyzed C=O hydrogenation and C–C hydrogenolysis, which could also avoid the coke formation. The EG selectivity was dependent on the synergy of WO x and Ni metal sites. In addition, this synergistic effect between the metal and WO x could promote lignin component degradation in direct conversion of untreated raw lignocellulosic biomass, obtaining the propyl monophenolics including guaiacylpropane, syringylpropane and p-n-propylphenol with a total yield of 17.3 wt% besides EG.
研究领域:
化学工程
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催化
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生物化工
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）