CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yu-Xuan Fu,Shu-Yi Huang,Ming-Shuai Sun,Yan Zhou,Dan-Dan Cai,Wen-Shuai Zhu,Wei Hui,Duan-Jian Tao
Current industrial catalysts for α-pinene hydrogenation suffer from harsh reaction conditions and poor selectivity to cis -pinane, primarily due to their inability to effectively adsorb α-pinene in a specific favorable configuration on the catalyst surface. In this study, a high-specific-surface-area, rod-shaped CeO 2 -supported ultra-fine Ru nanoparticle (average particle size of 4 nm) catalyst was synthesized via hydrothermal method for the highly stereoselective hydrogenation of α-pinene to cis -pinane. The resulting Ru/CeO 2 -H catalyst achieved an α-pinene conversion of 99.3 % and an impressive cis -pinane selectivity of up to 99.6 % under exceptionally low temperature (30°C), 0.6 MPa H 2 and 0.5 h with high TOF (1236 h −1 ). Density functional theory (DFT) calculations indicated that α-pinene preferentially adsorbs onto the Ru surface via the backside of its intramolecular dimethyl bridge. This particular adsorption mode lowers the energy barriers for further hydrogenation to generate cis -pinane. The oriented dimethyl-up configuration of α-pinene and ultra-low activation energy (12.04 kJ/mol obtained from kinetic tests) enable the highly selective production of cis -pinane at ambient temperature. Furthermore, the strong interaction between the CeO 2 -H support and highly dispersed Ru, combined with the ambient-temperature reaction conditions, effectively prevents metal nanoparticle agglomeration and coking, imparting the catalyst with exceptional stability. Notably, the catalyst was reused at least 15 times without observing any significant deactivation, demonstrating its significant potential for practical applications.
研究领域:
催化化学
·
材料科学
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Yuanjie Xu,Rong Chen,Hongqiao Lin,Qian Lv,Bo Liu,Lizhi Wu,Li Tan,Yihu Dai,Xupeng Zong,Yu Tang
Catalyst interface determines the activity and stability of partial oxidation of methane (POM) toward syngas under high temperatures crucially. Herein, Ni catalysts supported on CeO 2 were prepared under different pretreatment atmospheres to construct an optimal and robust interface. Ni/CeO 2 catalyst pretreated in H 2 (Ni/CeO 2 -H 2 ) exhibits the higher activity and the better stability than Ni/CeO 2 -Ar and Ni/CeO 2 -air catalysts. The Ni-O-Ce interfacial site in Ni/CeO 2 -H 2 catalyst shows the lower reduction temperature, indicating the enhanced H-spillover effect and enhanced oxidation resistance of Ni under POM conditions. Moreover, the XPS and in situ Raman results show that Ni/CeO 2 -H 2 contains more surface oxygen vacancies for adsorbing and activating oxygen, further contributing to the reaction activity. The in situ DRIFTS results indicate that the CH 4 could react with the lattice oxygen to form formate and carbonate, and further decompose to CO and CO 2 . These findings deepen the fundamental understanding of Ni/CeO 2 catalysts for POM reaction.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Small
·
2024
·
IF 13
Yangyang Ren,Beibei Li,Guichao Zhang,Zunming Lu,Lanlan Li,Xiaojing Yang,Xinghua Zhang,Xiaofei Yu
Improvement in the durable and active low-Pt nanocatalysts for oxygen reduction reaction (ORR) is the essential target for clean energy. Herein, an efficient CeO 2 supported PtCu alloy catalyst (PtCu/CeO 2 -C) for ORR in acid media is developed. The CeO 2 support can effectively anchor the PtCu particles and inhibit their migration during the long-life cycling, which is beneficial to the catalytic performance. According to the electrochemical experiments, the specific and mass activities of PtCu/CeO 2 -C are 1.09 mA cm −2 and 0.49 A mg Pt −1 at 0.9 V, which are 9.9 and 6.1 times as large as that of Pt/C, demonstrating its outstanding ORR activities in acid media. Moreover, the theoretical studies confirm that oxygen vacancies (V O ) as Lewis acid sites can facilitate the adsorption and dissociation of O 2 , regulate the electronic structure of Pt, and thus endow PtCu/CeO 2 -C with an efficient 4-electron ORR pathway. The results suggest that the rational design of supported Pt-based catalysts is of great significance for efficient ORR reaction.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yi-Ran Du,Rui Wang,Qing-Shan Niu,Yi-Yu Tao,Bao-Hua Xu
In this study, the bimetallic RuM-CeO 2 (M = Ni, Fe, Cu, K and Cs) catalysts were facilely fabricated by taking the commercially available CeO 2 (99.95 % metals basis, Aladdin, < 50 nm of diameter) as the support. They displayed distinct catalytic performance, especially the chemo-selectivity, on the methoxycarbonylation of styrene with CO and CH 3 OH. Impressively, Ru 2 Ni 0.6 -CeO 2 provided an up to 90.1 % yield of methyl phenylpropionate with satisfied linear selectivity (L/B = 91/9). The characterization and mechanistic results demonstrated that the doping of proper amount of Ni species enriches the local oxygen vacancy (Vö) at the surface but slightly reduces the charge at Ru sites, thereby modulating the interfacial Lewis acid − base pair (Ru-O-Ce-Vö) for catalysis. It thus enhances the CH 3 OH dissociation, leading to high coverage of OCH 3 species with low adsorption energy and relatively weak acidity. Further, the insertion of CO becomes readily due to the weak Ru-CO affinity at electron-deficient Ru center therein. As such, the apparent activation energies ( E a ) of styrene methoxycarbonylation over Ru 2 -CeO 2 (71.2 kJ mol −1 ) is nearly half-reduced by doping Ni element (Ru 2 Ni 0.6 -CeO 2 : 37.5 kJ mol −1 ). Meanwhile, the competitive side reactions at the surface of Ru 2 Ni 0.6 -CeO 2 is inhibited without sufficient acid strength and acid sites. Both aromatic olefins and cyclic olefins were well tolerated under such a system.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2018
·
IF 0
Xiaoqing Gao,Shanhui Zhu,Yongwang Li
The mild depolymerization of lignin into aromatic monomer is a grand challenge owing to the various aryl ether C–O bonds, particularly for the most abundant β-O-4, α-O-4 and 4-O-5 linkages. Rod-shaped CeO 2 supported AuPd bimetallic catalysts fabricated by sol-immobilization method presented robust alloy structure, as evidenced by TEM, XPS, UV–vis, and CO-DRIFTS. For the hydrogenolysis of C O bond model compound with formic acid, Au 1 Pd 1 /CeO 2 showed about 23.5 and 6 folds increase in activity compared with its monometallic counterparts Au/CeO 2 and Pd/CeO 2 , respectively. The outstanding performance was mainly ascribed to the increased adsorption ability of electron-deficient Pd for aromatic C–O bond. Additionally, formic acid-mediated Au 1 Pd 1 /CeO 2 has efficiently performed hydrogenolysis of real lignin into a variety of valuable monophenols, achieving 44.1% yield at low temperature.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Rui Liu,Xianhua Zhang,Tao Liu,Xian Yao,Zhijian Zhao,Chunlei Pei,Jinlong Gong
The oxygen species over oxygen carriers determine the reaction performance in chemical looping partial oxidation of methane (CLPOM). This paper describes the dynamic migration and reaction of oxygen species over ceria-supported NiO oxygen carrier for CLPOM. At initial reaction stage, Ni-O species could be consumed rapidly and cause the full oxidation of methane to CO 2 . Afterwards, the active Ni-O-Ce species dominates the methane partial oxidation to promote the syngas yield. It is found that CO formation rate is linearly related with the content of oxygen species over Ni-O-Ce. Furthermore, the lattice oxygen from CeO 2 would migrate through the bulk to complement the consumed Ni-O-Ce oxygen species. Eventually, 5NiO/(40CeO 2 -Al 2 O 3 ) exhibit nearly three times as high as methane reaction rate of CeO 2 /Al 2 O 3 and two times as high as CO formation rate of 5NiO/Al 2 O 3 . This work provides the comprehensive understanding of transport and reaction mechanism of oxygen species for chemical looping processes.
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2025
·
IF 6.5
Ziheng Zhen,Antai Li,Tiantian Xiao,Maoshuai Li,Jing Lv,Shouying Huang,Yue Wang,Xinbin Ma
Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO 2 supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO 2 exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO 2 catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H 2 molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.
研究领域:
催化化学
·
材料科学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Xiao-Chen Sun,Kun Yuan,Wang-De Hua,Zi-Rui Gao,Qian Zhang,Chen-Yue Yuan,Hai-Chao Liu,Ya-Wen Zhang
The metal–support interface plays a crucial role in heterogeneous catalysis. The modulation of the metal–support interaction (MSI) affords the possibility of promoting the catalytic efficiency per active site. Here, we report a strategy to modulate the interfacial interaction and then optimize the interfacial activity of Co/CeO2 catalysts for the water–gas shift reaction (WGSR) by a facile NH3 treatment process for the CeO2 support. The sample of Co/800N-CeO2 treated at 800 °C exhibited the highest reaction rate of 260 μmolCO/(gCo s), which was 23.8 times higher than the rate of the untreated Co/CeO2 sample. A combination of ex situ and in situ characterizations suggested that addition of the NH3 treatment process did not only weaken the metal–support interaction between the Co species and CeO2 support to strengthen CO adsorption and CO activation ability but also induced oxygen vacancy generation under reaction conditions to accelerate H2O activation. Both worked together in promoting the catalytic efficiency for the WGSR via the carboxyl pathway at a low temperature. It was worth mentioning that the N species of the CeO2 support introduced by the NH3 treatment was removed after changing the catalyst structure under reaction conditions. The interfacial structure was robust in a 60 h test at 400 °C due to the coexistence mechanism of carboxyl and formate pathways avoiding the poisoning effect of formate species on the active sites. The construction of active interfaces could be extended to Fe/CeO2 and Ni/CeO2 catalysts and could bring great promise in the design of the interfacial structure of supported catalysts in wide applications including chemical transformation reactions and industrial catalysis.
研究领域:
催化化学
·
材料科学
·
能源化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2018
·
IF 6.14
Shaodan Xu,Huanxuan Li,Jia Du,Junhong Tang,Liang Wang
We report the synthesis of subnanometric Au clusters with average diameters at 1.2 nm on a low-crystallinity CeO2 support (sub-Au/LC-CeO2), which exhibit high activities and selectivities in the aerobic oxidation of C–H bonds on a series of petroleum-derived hydrocarbons under solvent-free conditions. This phenomenon is strongly related to the maximized strong metal–support interactions between subnanometric Au and the LC-CeO2 support.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Wei Guo,Huanhao Chen
Nonthermal plasma (NTP)-assisted CO2 methanation can activate and convert stable CO2 molecules under ambient conditions as compared to conventional thermal catalysis (normal operation temperature up to 450 °C), which is a good technique to reduce CO2 emissions and simultaneously utilize the renewable energies like solar and wind. It is critical to develop a robust catalyst with good catalytic performance in order to make NTP catalytic CO2 methanation more competitive. Herein, we present a simple yet efficient synthesis of CeO2-supported Ni catalysts with yttrium (Y) as the promoter (i.e., Ni–Y/CeO2) via mechanochemical synthesis for efficient NTP catalytic CO2 methanation. The developed 7.5Ni–1Y/CeO2 catalyst demonstrated the highest energy efficiency values for CO2 conversion and CH4 yield, i.e., ∼57 gCO2 kWh–1 and ∼17 gCH4 kWh–1, respectively. The CO2-TPD and HRTEM results confirmed that the doped Y positively enhanced the basicity of the catalysts and also decreased the particle size of Ni nanoparticles, thus promoting the NTP catalytic activity of CO2 methanation. The catalyst displayed excellent short-term stability for plasma catalytic CO2 methanation over a 12 h on-stream evaluation, showing a CO2 conversion of 84.2 ± 1.8% and a CH4 selectivity of 83.3 ± 1.9%.
研究领域:
化学工程
·
环境科学
·
催化材料
✓ 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）