Nanoscale
·
2024
·
IF 5.8
Heyun Lin,Wenzhe Zhang,Huachen Shen,Hailing Yu,Yunlei An,Tiejun Lin,Liangshu Zhong
The catalytic behavior of CO hydrogenation can be modulated by metal–support interactions, while the role of the support remains elusive. Herein, we demonstrate that the presence of strong metal–support interactions (SMSI) depends strongly on the crystal phase of TiO2 (rutile or anatase) and the treatment conditions for the TiO2 support, which could critically control the activity and selectivity of Ru-based nanocatalysts for CO hydrogenation. High CO conversion and olefin selectivity were observed for Ru/rutile-TiO2 (Ru/r-TiO2), while catalysts supported by anatase (a-TiO2) showed almost no activity. Characterization confirmed that the SMSI effect could be neglected for Ru/r-TiO2, while it is dominant on Ru/a-TiO2 after reduction at 300 °C, resulting in the coverage of Ru nanoparticles by TiOx overlayers. Such SMSI could be suppressed by H2 treatment of the a-TiO2 support and the catalytic activity of the as-obtained Ru/a-TiO2(H2) can be greatly elevated from almost inactive to >50% CO conversion with >60% olefin selectivity. Further results indicated that the surface reducibility of the TiO2 support determines the SMSI state and catalytic performance of Ru/TiO2 in the CO hydrogenation reaction. This work offers an effective strategy to design efficient catalysts for the FTO reaction by regulating the crystal phase of the support.
研究领域:
催化化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 10
·2255
·
IF 4.2
Yan Cui,Zequan Zeng,Yaqin Hou,Shuang Ma,Wenzhong Shen,Zhanggen Huang
Noble metals have become a research hotspot for the oxidation of light alkanes due to their low ignition temperature and easy activation of C-H; however, sintering and a high price limit their industrial applications. The preparation of effective and low-noble-metal catalysts still presents profound challenges. Herein, we describe how a Ru@CoMn2O4spinel catalyst was synthesized via Ru in situ doping to promote the activity of propane oxidation. Ru@CoMn2O4exhibited much higher catalytic activity than CoMn2O4, achieving 90% propane conversion at 217 °C. H2-TPR, O2-TPD, and XPS were used to evaluate the catalyst adsorption/lattice oxygen activity and the adsorption and catalytic oxidation capacity of propane. It could be concluded that Ru promoted synergistic interactions between cobalt and manganese, leading to electron transfer from the highly electronegative Ru to Co2+and Mn3+. Compared with CoMn2O4, 0.1% Ru@CoMn2O4, with a higher quantity of lattice oxygen and oxygen mobility, possessed a stronger capability of reducibility, which was the main reason for the significant increase in the activity of Ru@CoMn2O4. In addition, intermediates of the reaction between adsorbed propane and lattice oxygen on the catalyst were monitored by in situ DRIFTS. This work highlights a new strategy for the design of a low-noble-metal catalyst for the efficient oxidation of propane.
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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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-10
·
IF 17.694
Zhou Jun,Gao Zhe,Xiang Guolei,Zhai Tianyu,Liu Zikai,Zhao Weixin,Liang Xin,Wang Leyu
Supports can widely affect or even dominate the catalytic activity, selectivity, and stability of metal nanoparticles through various metal-support interactions (MSIs). However, underlying principles have not been fully understood yet, because MSIs are influenced by the composition, size, and facet of both metals and supports. Using Ru/TiO 2 supported on rutile and anatase as model catalysts, we demonstrate that metal-support interfacial compatibility can critically control MSI modes and catalytic performances in CO 2 hydrogenation. Annealing Ru/rutile-TiO 2 in air can enhance CO 2 conversion to methane resulting from enhanced interfacial coupling driven by matched lattices of RuO x with rutile-TiO 2 ; annealing Ru/anatase-TiO 2 in air decreases CO 2 conversion and converts the product into CO owing to strong metal-support interaction (SMSI). Although rutile and anatase share the same chemical composition, we show that interfacial compatibility can basically modify metal-support coupling strength, catalyst morphology, surface atomic configuration, MSI mode, and catalytic performances of Ru/TiO 2 in heterogeneous catalysis.
研究领域:
催化
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材料科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2023
·
IF 3.7
Jia-Qi Chen,Xu-Xu Ye,Da Zhou,Yan-Xia Chen
Electrochemical reduction is a potential solution to eliminate nitrate in wastewater; however, the poor activity and product selectivity of traditional electrocatalysts impede its large-scale application. Herein, we report a new catalyst of Cu-modified Ru nanoparticles (Cu-modified Ru/C NPs) prepared by underpotential deposition (UPD) of Cu atoms onto Ru NPs, which shows good nitrate reduction kinetics and NH3 selectivity. To unravel the enhancing mechanism, the impact of Cu coverage on nitrate reduction and the formation of possible products/intermediates as well as the competition of side products H2 have been investigated systematically by tracking the reverse oxidation of such species using rotation ring disk electrode (RRDE) combined with cyclic voltammetry. Our results reveal that the Cu-modified Ru/C NPs perform NH3 yield of 23.7 μmol h–1 cm–2 and 95% Faradaic efficiency, which is better than Ru/C NPs (6.0 μmol h–1 cm–2 with Faradaic efficiency of 66%); This enhancement of modified Cu atoms toward nitrate reduction results from synergetic effects: (i) Cu blocks the hydrogen evolution reaction (HER) sites on Ru surface; (ii) Cu accelerates the rate of nitrate reduction to nitrite; (iii) the enhanced nitrite reduction activity of Cu sites on Ru substrate is probably a result of changes in electronic structure of Cu.
研究领域:
环境科学
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催化
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电化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2016
·Vol. 18
·期 11
·3370-3377
·
IF 8.506
Wenjing Yang,Haiyang Cheng,Bin Zhang,Yan Li,Tong Liu,Mingli Lan,Yancun Yu,Chao Zhang,Weiwei Lin,Shin-ichiro Fujita,Masahiko Arai,Fengyu Zhao
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied with a homogeneous RuCl2(PPh3)3 catalyst in supercritical CO2 (scCO2). The conversion of LA was observed to increase with CO2 pressure and the possible reasons for this rate acceleration were discussed, including the molecular interactions of CO2 with the reacting and catalytic species as well as the acidity and phase behavior of the reaction mixture. The interaction between CO2 and RuCl2(PPh3)3 was significant, which resulted in the production of an active RuHCl(CO)(PPh3)3 complex and thus enhanced the rate of hydrogenation in the presence of CO2.
研究领域:
化学工程
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催化化学
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产品关联
DOI
高影响因子
RSC Advances
·
2018
·Vol. 8
·期 71
·40989-40995
·
IF 2.936
Ruifeng Wang,Lungang Chen,Xinghua Zhang,Qi Zhang,Yuping Li,Chenguang Wang,Longlong Ma
Novel catalytic material with high catalytic activity and hydrothermal stability plays a key role in the efficient conversion of levulinic acid (LA) to γ-valerolactone (GVL) in water. In this study, mixed oxides Al2O3–TiO2, Al2O3–MoO3 and Al2O3–Co3O4 were synthesized by co-precipitation using aqueous solution of NaOH as precipitant. Ru catalysts supported on mixed oxides were prepared by impregnation method and their catalytic performances were tested in the hydrogenation of LA to GVL on a fixed bed reactor. The physicochemical properties of the catalysts were characterized by XRD, H2-TPR, NH3-TPD, and BET techniques. The TiO2 component significantly affected the acidity of the catalyst, and thus its catalytic activity for the GVL yield was affected. The desired product GVL with a yield of about 97% was obtained over the Ru/Al2O3–TiO2 catalyst under mild conditions (WHSV = 1.8 h−1, T = 80 °C). Moreover, the catalyst Ru/Al2O3–TiO2 exhibited excellent thermal stability in the test period of time.
研究领域:
催化
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化学工程
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材料科学
✓ 已验证
DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2022
·
IF 4.177
Kang Hu,Ping Liu,Ziqing Zhang,Ji Bian,Guowei Wang,Hongjun Wu,Hui Xu,Liqiang Jing
g-C3N4 is a promising photocatalyst for CO2 conversion owing to its outstanding reduction potential. However, its shallow valence band position and sluggish water oxidation reaction restrict the overall CO2 photoreduction process. Herein, g-C3N4 nanosheets are first doped with B through thermal treatment of mixed NaBH4 and subsequently modified with highly dispersed Ru-oxo clusters by using tailored chitosan oligomers. The optimal Ru-oxo modified B-doped g-C3N4 exhibits an exceptional photocatalytic CO2 conversion rate with 22-fold improvement compared with pristine CN. Based on the results of electron paramagnetic resonance, atmosphere-controlled surface photovoltage spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it is confirmed that the improved photoactivities are attributed to the downward shift of the valence band to obtain the strong driving force for water oxidation along with extension of the visible light response region by B doping and to the capture of photogenerated holes to enhance charge separation and then to accelerate the water oxidation process from the modified Ru-oxo clusters.
研究领域:
材料科学
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化学
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环境科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Ying Yang,Dongcheng Ren,ChunLi Shang,Zhongzhen Ding,Xinruo Luo
Direct conversion of cellulose to high yield 1,2-propylene glycol (1,2-PG) is amazing in the biomass valorization to diols, since this process is atom-economic, carbon neutral, and the produced 1,2-PG has a large market demand. However, it is very challenging to control cellulose hydrogenolysis owing to high reactivity of intermediates (like glucose) and metal-acid repelling, leading to decreased selectivity of metal-acid multi-functional catalysts. Aimed at this, we herein developed a highly selective metal-acid catalyst (Ru/NC@void@MC-SO 3 H) with site isolated Ru clusters (1.4 nm) on the core and sulfoacids on the shell in a yolk-shell nanoreactor by a layer-by-layer assembly before chemical transformation. The spatial isolation of metal and acid sites integrated in a mesoporous yolk-shell nanoreactor not only facilitates the metal-acid synergism in hydrolysis, isomerization/hydrogenolysis and hydrogenation cascade reactions, but also provides a designated diffusion pathway that is favorable for reaction species. As expected, the elaborately fabricated Ru/NC@void@MC-SO 3 H proves to be highly selective to 1,2- PG (38 % yield), delivering a productivity of 342.86 mol h −1 g Ru –1 and an extremely high turnover number of 173264, outperforming the state-of-art metal-acid catalysts for cellulose hydrogenolysis to 1,2-PG. Our characterization and performance test suggest that sulfoacids are mainly responsible for cellulose hydrolysis, while N -stabilized Ru centers contribute to the glucose isomerization to fructose and its further hydrogenolysis to dihydroxyacetone, followed by hydrogenation to 1,2-PG on metallic Ru species. The acidity and basicity optimized for site isolated Ru/NC@void@MC-SO 3 H is beneficial to balance intermediate reactions, rendering a higher selectivity to target 1,2-PG. The concept illustrated in this study will provide a guide for the development of other site isolated multi- functional catalysts towards cellulosic biomass conversion and other cascade reactions.
研究领域:
催化化学
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生物质转化
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材料科学
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产品关联
DOI
高影响因子
Catalysts
·
2022
·Vol. 12
·期 12
·1625
·
IF 4.501
Bo Chen,Zhi-Ze Cao,Zhi-Jun Diao,Liang-Qiu Huang,Si-Jia Zhao,Hong Yuan,Jia-Meng He
Hydrogenolysis via targeted depolymerization of C–O linkages is a techno-economic beneficial process for converting lignin into highly valuable chemicals and clean fuels. In this work, a macroporous silicalite-1 (S-1) array-supported Ru-Ni metallic phosphide composite (Ru-Ni12P5/S-15) was prepared as a catalyst and hydrogenolysis activity under relative mild conditions was investigated using a series of compounds containing ether linkages as lignin-related model compounds. The Lewis acid sites originating from the unreduced Ru species and the macroporous geometry of S-1 significantly influenced hydrogenolysis activity and product selectivity. Analysis of the mechanism demonstrated that both the aryl ether and aliphatic ether linkages were directly hydrogenated over Ru-Ni12P5/S-15. 2D-HSQC-NMR spectroscopy demonstrated that the ether linkages of lignin were efficiently cleaved by Ru-Ni12P5/S-15. Furthermore, the obtained liquid hydrogenolysis products are high value-added chemicals used for pharmaceutical production and can be facilely tuned via the reaction conditions.
研究领域:
催化化学
·
可再生资源转化
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 3
·1152-1164
·
IF 10.182
Jiahui Zhan,Rui Hu,Xi Luo,Cheng Zhang,Gang Luo,Jiajun Fan,James H. Clark,Shicheng Zhang
Cyclohexanol is an essential intermediate in the chemical industry for the synthesis of nylon and other materials, but the direct hydrogenation of phenol to produce cyclohexanol is problematic owing to excessive energy consumption associated with the harsh reaction conditions. In this regard, novel composite catalysts (Ru/Nb2O5-nC18PA) coated with octadecylphosphonic acid (C18PA) were prepared via an impregnation method to be applied for the efficient hydrogenation of phenol to produce cyclohexanol in a biphasic system consisting of water and decalin solvent. Under a hydrogen pressure of 12 bar and 80 °C, nearly 100% conversion of phenol and 93% yield of cyclohexanol were achieved within 4 hours. With the introduction of more Lewis acid sites the aromatic ring is activated, which promotes the HYD (hydrogenation) path of phenol, thereby giving improved selectivity to cyclohexanol. A mechanism-exploration experiment was carried out and showed that the strong binding effect between the surface of the Ru/Nb2O5-nC18PA catalysts and the benzene ring allows the aromatic ring in phenol to be hydrogenated, increasing the selectivity to cyclohexanol. This biphasic catalytic system enhances the potential value of lignin via the catalytic hydrogenation of lignin-derived phenols.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Wenming Liu,Shenyou Yang,Qiuli Zhang,Tianyao He,Yiwei Luo,Jinxiong Tao,Daishe Wu,Honggen Peng
Herein, a series of nano-flower sheet-like alumina spheres (NF-Al 2 O 3 ) with rich unsaturated pentacoordinate Al 3+ sites stabilizing Ru-CeO x catalysts were designed and synthesized for catalytic total oxidation of one typical light alkanes (propane, C 3 H 8 ). The 90 % conversion temperature (T 90 ) and the apparent activation energy (Ea) of Ru-Ce 7 /NF-Al 2 O 3 modified by 7 wt.% of CeO 2 were as low as 207 °C and 56.7 kJ mol −1 , respectively. In addition, it also exhibited superior water, sulfur and carbon dioxide resistance and recycling performance. The excellent catalytic performance of propane total oxidation over Ru-CeO x /NF-Al 2 O 3 is mainly attributed to NF-Al 2 O 3 has rich unsaturated pentacoordinate Al 3+ sites can anchor the Ru-CeO x active species. The anchoring effect of Al 3+ penta on the metal active unit can effectively promote the dispersion of Ru-CeO x active species and stabilize the electronic valence state of Ru 0 . The degradation of C 3 H 8 over Ru-CeO x /NF-Al 2 O 3 conformed to the Mars-van-Krevelen mechanism through two different pathways as revealed by the in situ DRIFTS.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Chao Miao,Shumei Chen,Kaixuan Shang,Lixing Liang,Jing Ouyang
The dry reforming of methane (DRM) is a new potential technology that converts two major greenhouse gases into useful chemical feedstocks. The main challenge faced by this process is maintaining the catalyst with high catalytic activity and long-term stability. Here, a simple and effective preparation route for the synthesis of functional nanomolecular sieve catalysts (NiRuxCZZ5) from kaolinite tailings was developed for dry reforming of methane with CO2. The silica monoliths with flower-like spherical and micropore structures (ZSM-5) were prepared by crystal growth method, and the metal components were loaded by ultrasonic-assisted impregnation method. The NiRu0.5CZZ5 catalyst exhibited excellent catalytic performance (maxmium CO2 and CH4 conversions up to 100 and 95.6%, respectively) and very good stability (up to 100h). The interfacial confinement and the strong support interaction are principally responsible for the excellent catalytic activity of the catalyst. The in situ DRIFTS was used to elucidate the possible carbon conversion steps, and stable surface intermediates were also identified.
研究领域:
催化化学
·
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）