INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2022
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IF 4.326
Mingshuai Sun,Fumin Wang,Guojun Lv,Xubin Zhang
Overhydrogenation to ethane is most undesired in selective hydrogenation of acetylene. Monometallic Pd supported on common oxide supports such as alumina and silica suffers from susceptibility of ethane formation, and the ethylene selectivity is usually unsatisfactory. Herein, Fe5C2 was carefully synthesized and employed as a new kind support doped with a (5–600) ppm level of Pd for selective hydrogenation of acetylene. The catalyst with appropriate Pd loadings exhibited more efficient ethane suppression and much higher ethylene selectivity than the traditional α-Al2O3 supported Pd catalyst, with full acetylene conversion under 240 °C, and maintained good stability after a 200 h tolerance test. Characterization and DFT calculation results reveal that the excellent ethylene selectivity is mainly derived from the special interaction between Pd atoms and the Fe5C2 support. Hydrogenation of ethylene to ethane needs to cross extremely high activation energy barriers on the catalyst surface, and ethylene desorption more easily occurs on it. Doping the appropriate amount of Pd atoms on the Fe5C2 surface can increase the obstacle for polymerization and will cause the unsaturated C2 species to be more inclined to be hydrogenated into C2H4. This synergy effect also acts as a guide in alkane suppression for selective hydrogenation of other alkynes.
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
ACS Materials Au
·
2022
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IF 0
Qingsong Luo,Hai Wang,Liang Wang,Feng-Shou Xiao
Selective hydrogenation of acetylene to ethylene is an industrially important process to purify the raw ethylene stream for producing high-grade polyethylene. The supported Pd catalyst exhibits superior activity for acetylene hydrogenation but suffers from poor ethylene selectivity because of the easy overhydrogenation to produce ethane. Here, we report that the PdCu alloy nanoparticles within siliceous zeolite crystals effectively tuned Pd-catalyzed overhydrogenation into semihydrogenation. This catalyst displayed an ethylene selectivity of 92.9% with a full conversion of acetylene. Mechanism studies reveal that the zeolite fixation stabilized the alloyed structure, where the electron-enriched Pd surface benefits the rapid ethylene desorption to hinder the deep hydrogenation. This work provides an efficient strategy for a rational design of bimetallic metal catalysts for selective hydrogenations.
研究领域:
催化化学
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材料科学
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纳米技术
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DOI
ACS Sustainable Chemistry & Engineering
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2020
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IF 7.632
Qingqing Guan,Jian Zhang,Liang He,Rongrong Miao,Yuzhen Shi,Ping Ning
As one of the organic carbon-rich feedstocks, Miscanthus sinensis is an interesting candidate for producing many high-value materials and chemicals. In this study, M. sinensis-derived activated carbon (msAC) particles with ca. 3.4 nm average pore size have been prepared by a simple carbonation method for supporting Pd nanoparticles (NPs) to hydrogenate acetylene. Catalytic test results showed that the 0.25% Pd/msAC catalyst could convert ∼99.9% of acetylene with ∼99.9% of ethylene selectivity. The life test result strongly demonstrated that the catalyst had a good durability for long-term (>100 h) acetylene hydrogenation with high conversion (∼99.9%) and ethylene selectivity (∼93.1%) at 260 °C with a space velocity of 80,000 h–1. The characterization results indicated that the msAC with the micro- and nanoscale pore structure and uniformly distributed oxygen-containing functional groups could efficiently disperse Pd nanoparticles and promote their Pd (111) crystal plane exposure. The above structure nature was co-contributing to the catalyst to choose the energetically favorable path for efficient acetylene hydrogenation and ethylene desorption. This work opens up valuable insights into the high-value utilization of M. sinensis biomass to design an efficient isolated Pd NP catalyst.
研究领域:
材料科学
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催化化学
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生物质利用
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产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
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2025
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IF 4.7
Changjin Xu,Yinglei Liu,Huiqing Guo,Chun Du,Gaowu Qin,Song Li
The ability to finely tune the nuclearity of active metal sites is critical for designing highly selective catalysts, especially for hydrogenation processes. In this work, we developed a novel PdCu catalyst with an ordered body-centered cubic (BCC) structure, enabling precise control over Pd nuclearity to optimize selectivity. Using a facile polyol synthesis method, we modulated the Pd coordination environment, reducing the Pd–Pd coordination number from 3 (disordered face-centered cubic, FCC) to 0 (ordered BCC), thereby achieving full isolation of Pd by the surrounding Cu atoms. This structural transformation enhances hydrogen spillover and weakens ethylene adsorption, resulting in superior activity for the selective hydrogenation of acetylene to ethylene. The ordered PdCu supported on Al2O3 (o-PdCu/Al2O3) achieved a 99% acetylene conversion with an 84.5% ethylene selectivity at near-room temperature. This work highlights the importance of controlling atomic-scale nuclearity in metal catalysts and provides a promising strategy for improving the catalytic efficiency and selectivity in industrially significant processes.
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
ACS Catalysis
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2021
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IF 13.084
Yu Wang,Boyang Liu,Xiaocheng Lan,Tiefeng Wang
For supported metal catalysts, subsurface sites can significantly influence the adsorption and reaction behaviors on surface sites via the electronic effect and geometric effect. Subsurface carbon in PdCx has been proven to be an effective selectivity promoter in acetylene semihydrogenation. Herein, we theoretically calculated the reaction trajectory on Ni3ZnC0.7 and designed a metal–organic framework-layered hydroxide salt-derived synthesis strategy for the Ni3ZnC0.7/C catalyst. The formation of the flake-like Ni3ZnC0.7 phase was monitored by in situ X-ray diffraction (XRD) and confirmed by XRD, transmission electron microscopy, and selected area electron diffraction characterizations. In acetylene semihydrogenation, the Ni3ZnC0.7/C catalyst had 85% ethylene selectivity even at 100% acetylene conversion, supporting the conclusions from density functional theory calculations. The green oil selectivity was controlled below 2%. All results indicated that incorporating carbon atoms in the subsurface sites significantly enhanced the ethylene selectivity in acetylene semihydrogenation.
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
高影响因子
APPLIED CATALYSIS A-GENERAL
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2018
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IF 4.521
Yiqi Xu,Yishu Jiang,Hao Xu,Qingtao Wang,Weimin Huang,Haihua He,Yuanyuan Zhai,Shuxia Di,Lingling Guo,Xiaoliang Xu,Jia Zhao,Feng Feng,Qunfeng Zhang,Xiaonian Li
Designing the electron-rich palladium active site is of great importance to enhance the selectivity of ethylene in acetylene semi-hydrogenation. In this work, ionic liquids, the effective electronic modifier, were mingled with palladium solution to be immobilized on Al 2 O 3 by incipient impregnation method. X-ray photoelectron spectra characterization was conducted to characterize the structure of catalysts, suggesting that some ionic liquids can form unique carbene structure. The catalytic results showed that those immobilized ionic liquids that can form unique carbene structure exhibited much higher selectivity of ethylene than those cannot. The above results were obtained because carbene can donor the electron to palladium, enriching the electron density of palladium and therefore facilitating the desorption of ethylene. The findings of the unique carbene structure derived from ionic liquids in this work provide an efficient strategy to design the catalyst to improve the selectivity of the intermediate in other partial hydrogenationreactions.
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
高影响因子
ACS Applied Nano Materials
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2019
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IF 0
Haijun Chen,Zhimin Li,Zhaoxian Qin,Hyung J. Kim,Hadi Abroshan,Gao Li
Selective conversion of acetylene impurities to ethylene is a major step in processing chemical feedstock in industry. Currently, this step is widely performed through the catalytic hydrogenation of acetylene over palladium-based materials. Because of a lack of selectivity, however, this method suffers from the formation of ethane to a considerable extent. Herein, we present gold nanoclusters encapsulated in microporous silica as robust catalysts for the hydrogenation of acetylene with 98% selectivity toward ethylene formation. These encapsulated catalysts are designed to avoid the aggregation of nanoclusters during thermal pretreatment at ∼500 °C by maintaining an average nanocluster size of around 1.6 nm. This approach yields an acetylene conversion efficiency of ∼95% at 280 °C. The catalysts are characterized by UV–vis, Fourier transform infrared, NMR, and X-ray spectroscopies as well as density functional theory. Analysis shows that preservation of the nanoscale size of the gold particles at operating temperature coupled with the maintenance of positive charges on the surface active sites induced by the presence of electronegative species of microporous silica can be utilized as an efficient strategy to significantly improve acetylene activation for the semihydrogenation reaction.
研究领域:
化学工程
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催化科学
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材料科学
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产品关联
DOI
ACS Applied Nano Materials
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2020
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IF 0
Siyu Kuang,Minglu Li,Rong Xia,Lei Xing,Yaqiong Su,Qun Fan,Jinping Liu,Emiel J.M. Hensen,Xinbin Ma,Sheng Zhang
The electrochemical carbon dioxide reduction reaction (CO2RR) is a promising solution to the current environmental and energy issues. Cu is the only metal catalyst able to convert CO2 into high-value-added hydrocarbons. However, Cu catalysts tend to degrade with the decrease in the hydrocarbon selectivity under operation conditions. Herein, we monitored the morphological evolution of Cu nanocatalysts and correlated with changes in the selectivity of hydrocarbon products during electrochemical CO2 reduction. Initial Cu nanospheres quickly reconstructed into nanocubes within 1 h of CO2 electrolysis and then gradually turned into even smaller irregular nanoparticles. Interestingly, the above unstable Cu nanocube offered the maximum ethylene selectivity. We successfully stabilized these Cu nanocubes using a 2D graphene surface doped with nitrogen to achieve high ethylene selectivity over 24 h. Our X-ray photoelectron spectroscopy (XPS) and density-functional theory (DFT) investigations show that the strong interaction between Cu and pyridinic nitrogen on the 2D graphene surface plays a key role in stabilizing Cu nanocubes.
研究领域:
材料科学
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电化学
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催化反应
✓ 已验证
DOI
CERAMICS INTERNATIONAL
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2023
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IF 5.2
Minghan Qin,Shixian Zhang,Wang Sun,Chunming Xu,Jinshuo Qiao,Zhenhua Wang,Shuying Zhen,Kening Sun
The electrocatalytic conversion of ethane to ethylene is an important industrial process since ethylene is useful for the production of various chemical intermediates and polymers. However, this process often requires high temperatures. Metal-oxide heterogeneous interfaces constructed by in-situ exsolved process under reducing conditions would be favorable for promoting the catalyst activity, selectivity, and stability of ethane conversion to ethylene. Herein, Sr 1.95 Fe 1.4 Co 0.1 Mo 0.5 O 6-δ (abbreviated as SFCoM) was prepared as a novel anode material of solid oxide electrolysis cells (SOECs) for green ethylene production by electrochemical oxidative dehydrogenation of ethane. After reduction, nano CoFe particles were in-situ exsolved on SFCoM oxides to form a nano alloy-oxide heterostructure (CoFe@SFCoM) with large numbers of reactive sites, relevant for improving the conversion rate of ethane and the yield of ethylene. At 800 °C, the single cell based on CoFe@SFCoM anode exhibited a current density of 1.89 A cm −2 at 1.6 V with an ethane conversion rate of 36.4% and corresponding ethylene selectivity of 94.5%. After 50 h of testing, the electrolysis current density(∼0.5 A cm −2 ) and ethylene yield(∼18.43%) of the single cell did not change significantly, showing good stability. In sum, CoFe@SFCoM looks very promising for future use as a SOECs anode for the electro-catalytic conversion of ethane to ethylene.
研究领域:
材料科学
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电化学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Yingna Wang,Zilong Liu,Yuanpei Lan,Chaoyi Chen,Wei Zhang
The removal of small amounts of phenylacetylene from styrene is a crucial step in the production of high-quality styrene feedstocks. In the presence of a large amount of styrene and a small amount of phenylacetylene, achieving and maintaining high selectivity of styrene remains a significant challenge. In this work, a catalyst denoted as Pd 1.25 -Fe-N-C/VC was designed and synthesized with remarkably low Pd loading (the actual Pd content was 0.96 wt%). The catalyst exhibited a satisfactory selectivity for styrene (>95 %) and maintained high selectivity levels (>90 %) in the semi-hydrogenation of phenylacetylene even with prolonged reaction time. Pd nanoparticles (NPs) were well distributed and securely anchored onto the Fe-N-C/VC support with a hierarchical mesoporous structure, which obtained from the pyrolysis of a hexagonal star-like Fe-doped zeolitic imidazolate framework with vitamin C surfactant (Fe-doped ZIF/VC). The remarkable catalytic properties may be partly ascribed to the effective synergy effect of the uniformly well-dispersed Fe-N x (x represents the coordination number) with Pd active centers, which could modulate the adsorption kinetics of the reactant alkynes and alkenes and thus enhancing the selectivity towards styrene. Meanwhile, the hierarchical mesoporous structure is beneficial for the mass transfer, which can effectively promote the interactions between the reactants and active centers. Possible mechanism for the selective hydrogenation of phenylacetylene catalyzed by Pd 1.25 -Fe-N-C/VC was also illustrated. Moreover, the Pd 1.25 -Fe-N-C/VC catalyst exhibited sustained catalytic activity and selectivity even after four continuous cycle tests, showing notable reusability and stability. This work may offer a promising approach for creating highly efficient Pd-based catalysts with remarkably low Pd loading for phenylacetylene semi-hydrogenation.
研究领域:
化学工程
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催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
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2020
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IF 12.35
Xianxian Shi,Yue Lin,Li Huang,Zhihu Sun,Yong Yang,Xiaohong Zhou,Evgeny Vovk,Xinyu Liu,Xiaohui Huang,Mei Sun,Shiqiang Wei,Junling Lu
Metal particle size plays essential roles in metal-catalyzed heterogeneous reactions. Reducing the particle size from a few nanometers down to atomically dispersed single atoms alters both the morphology and electronic property of the metal enormously, thus greatly modulating its catalytic performance. Detailed investigation of the particle size effect as well as taking account of a metal single-atom catalyst (SAC), the frontier in heterogeneous catalysis, can provide a deeper insight into structure–activity relations and facilitate the rational design of advanced metal catalysts. However, such studies have been rarely reported. Herein, Cu single atoms and nanoparticles with different sizes of about 3.4, 7.3, and 9.3 nm were synthesized on an alumina support using atomic layer deposition. Comprehensive microscopic and spectroscopic characterization shows that the Cu single atoms remain very stable and have 1+ valence state after reduction at 300 °C in hydrogen. In semihydrogenation of acetylene in excess of ethylene, we show that a decrease in the Cu particle size reduces the activity considerably but gradually improves both the ethylene selectivity and durability. In particular, the Cu SAC exhibits the highest ethylene selectivity of 91% at the complete conversion along with excellent long-term stability for at least 40 h, in sharp contrast with the rapid deactivation on Cu nanoparticle catalysts. In situ thermogravimetry measurements further reveal that coke formation on Cu1 SAC is significantly suppressed by up to ∼89% compared to that on the 9.3 nm Cu nanoparticle catalysts. In brief, our findings demonstrate that SACs can be promising candidates for selective hydrogenation reactions in terms of high selectivity and high coking resistance.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
ACS Catalysis
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2025
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IF 13.1
Xiaohu Ge,Jinquan Ming,Yundao Jing,Nina Fei,Lingling Guo,Yueqiang Cao,Hao Jiang,Jing Zhang,Gang Qian,Xinggui Zhou,Xuezhi Duan
Designing high-efficiency and cost-effective catalysts for acetylene semihydrogenation holds significance for the production of polymer-grade ethylene in the chemical industry but remains difficult. In this study, we demonstrate an efficient synthesis of the CoSb intermetallic catalyst achieved through the in situ capture of molten Sb by Co, aiming to identify the Co-based catalysts for acetylene semihydrogenation. Combined investigations using X-ray diffraction, aberration-corrected high-resolution scanning transmission electron microscopy, and X-ray absorption spectroscopy demonstrate the presence of the pure CoSb intermetallic phase in the synthesized CoSb catalyst. The CoSb intermetallic catalyst, with a well-defined atomic arrangement and fine-regulated electronic properties, delivers 94.0% ethylene selectivity at ∼100% acetylene conversion. Temperature-programmed experiments and in situ spectroscopic studies, combined with theoretical calculations, unravel that the good hydrogenation performance arises from the moderate σ-binding of acetylene and easy desorption of ethylene on the fine-tuned Co active sites by Sb. These insights would be valuable for the creation of high-efficiency catalysts for acetylene semihydrogenation and potentially for other alkynes as well.
研究领域:
化学工程
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催化材料科学
✓ 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）