APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
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IF 19.503
Kaiyi Su,Yehong Wang,Chaofeng Zhang,Zhuyan Gao,Jianyu Han,Feng Wang
Herein, we reported the tuning of dominant products in the photocatalytic hydrogen transfer reaction over Pt/Nb 2 O 5 photocatalysts, using a support-induced modification strategy. In the photocatalytic conversion of phenylacetylene with ethanol as a probe reaction, the dominant product was styrene over Pt/2D Nb 2 O 5 nanoplates; in contrast, H 2 was the main product over the Pt/bulk Nb 2 O 5 . Compared to the metallic Pt species over bulk Nb 2 O 5 , the positively charged Pt (Pt δ+ ) species over 2D Nb 2 O 5 nanoplates contributed to the reduction of phenylacetylene, which was revealed by CO adsorbed Fourier transform infrared spectra. Furthermore, the present Pt δ+ species were due to the formation of Pt δ+ –O–Nb structure via oxygen transfer of 2D Nb 2 O 5 nanoplates, which was verified by the results of X-ray photoelectron spectra and H 2 temperature-programmed reduction. This work sheds light on the design and application of Nb-based catalysts in the transfer hydrogenation of organics in photocatalysis.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
GREEN CHEMISTRY
·
2013
·Vol. 15
·期 9
·2525-2531
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IF 6.828
Dongshun Deng,Yang Yang,Yutong Gong,Yi Li,Xuan Xu,Yong Wang
Palladium nanoparticles supported on a mesoporous graphitic carbon nitride, Pd@mpg-C3N4, has been developed as an effective, heterogeneous catalyst for the liquid-phase semihydrogenation of phenylacetylene under mild conditions (303 K, atmospheric H2). A total conversion was achieved with high selectivity of styrene (higher than 94%) within 85 minutes. Moreover, the spent catalyst can be easily recovered by filtration and then reused nine times without apparent lose of selectivity. The generality of Pd@mpg-C3N4 catalyst for partial hydrogenation of alkynes was also checked for terminal and internal alkynes with similar performance. The Pd@mpg-C3N4 catalyst was proven to be of industrial interest.
研究领域:
化学工程
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催化科学
✓ 已验证
DOI
高影响因子
HETEROCYCLIC COMMUNICATIONS
·
2023
·Vol. 29
·期 1
·
IF 2.3
Mingyu Zhang,Yuqi Tang,Rui Xu,Dong Yan,Shuangping Xu,Yanqing Qu,Jingyu Xu,Hongge Jia
Due to the chemical properties of Group VIII transition metals and their importance in catalytic processes, the reactions of rhodium and its neighboring organic complexes have received much attention as model systems. In the present experiments, we successfully prepared two new rhodium complexes named [Rh(cod)(TTP)Cl] and [Rh(cod)(CDP)Cl] using tri( o -tolyl)phosphine and clohexyldiphenylphosphine as ligands, respectively, and the proofs of their structures were completed using 1 H NMR and 13 C NMR. Subsequently, it was applied to the polymerization reaction of phenylacetylene (PA), and the effects of different solvents, time, and temperature on the yield and molecular weight of the polymerization reaction products were discussed. The experimental results show that both complexes can play a catalytic role in the polymerization of PA. From the point of view of polymer molecular weight, the best reaction conditions for both catalysts were 3 h at 20°C in THF solvent (molecular weight up to 2.40 × 10 5 ). From the point of view of yield, the best reaction conditions for both catalysts were 4 h at 35°C in THF solvent (yield up to 89.2%).
研究领域:
化学
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材料科学
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DOI
高影响因子
ChemNanoMat
·
2021
·Vol. 7
·期 11
·1213-1220
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IF 3.154
Yang Liu,Yong Zhao,Yulong Zhao,Peng Jiang
Graphical We report an efficient and robust Cu-decorated Rh/TiO 2 catalyst that improves the styrene selectivity in selective hydrogenation of phenylacetylene. The appropriate Cu coverage is found to modulate the electronic states of surface Rh atoms and changes the Rh exposed active sites, thus mitigating the overhydrogenation and enhancing the selectivity. Phenylacetylene as an impurity in styrene is poisonous to catalysts for styrene polymerization in the production of polystyrene plastics. The selective hydrogenation of phenylacetylene to styrene is an industrially promising route to overcome this challenge yet lacks cost-effective catalysts to prevent the overhydrogenation of styrene to ethylbenzene. In this work, we report an efficient and robust copper-decorated Rh/TiO 2 catalyst for the selective hydrogenation of phenylacetylene to styrene. By optimizing the copper coverage on TiO 2 supported Rh nanoparticles, we achieved a selectivity of 83% towards styrene formation at a phenylacetylene conversion of 93%. The appropriate Cu coverage is found to modulate the electronic states of surface Rh atoms and changes the Rh exposed active sites, weakening the binding strength of alkene and hydrogen intermediates on Rh and thus mitigating the overhydrogenation and enhancing the selectivity for styrene generation. This work offers insights on the rational design of efficient Rh-based bimetallic catalysts for selective hydrogenation of phenylacetylene to styrene.
研究领域:
化学工程
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催化材料
✓ 已验证
DOI
高影响因子
CATALYSIS LETTERS
·
2019
·Vol. 149
·期 2
·361-372
·
IF 2.372
Liu Yanan,Yang Zhao,Zhang Xinyi,He Yufei,Feng Junting,Li Dianqing
Abstract A series of CeO 2 with the morphology of nanocube (NC), nanopolyhedron (NP) and nanorod (NR) were synthesized by hydrothermal method as substrates to support monometallic Au catalysts. Insight into support morphology-dependent the property of active component and catalytic behavior for the selective hydrogenation of phenylacetylene has been performed. Specifically, nanocube ceria could disperse monometallic Au nanoparticles due to a large amount of low coordinated sites that readily generated the strong interaction for anchoring active metal, whereas the polyhedron and rod-like ceria supported Au nanoparticles possessed large size and wide particle distribution. As expected, well-dispersed and stable Au/CeO 2 nanocube demonstrated 83% of selectivity towards styrene when the conversion of phenylacetylene reached 90%, which was much higher than that of others. Preferable activity was mainly ascribed to small size of Au nanoparticles, which facilitated the adsorption/dissociation of hydrogen considered as the rate-determining step. Enhanced selectivity was due to the electronic effect that caused by strong interaction between Au and cubic CeO 2 , which also contributed to good stability. This work not only provides a facile method for the preparation of highly dispersed and efficient Au/CeO 2 catalysts by modulating the morphology of support, but also offers a novel idea for the fabrication of other highly dispersed supported metal catalysts with enhanced behavior in heterogeneous catalysis. Graphical Abstract
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Lei Yang,Shiyi Yu,Chong Peng,Xiangchen Fang,Zhenmin Cheng,Zhiming Zhou
A series of nonprecious monometallic Ni/AlSBA-15 and bimetallic Ni M (M = Zn, Ga, Cu, or Fe)/AlSBA-15 catalysts were prepared using a urea precipitation method and applied to the semihydrogenation of phenylacetylene. The catalysts were characterized by various techniques, showing that the Ni particle size of catalyst can be tuned by adjusting the Al content, and NiZn and NiGa supported catalysts exhibited geometric and electronic effects that originated from the bimetallic alloy. Among all the catalysts studied, NiZn 3 /AlSBA-15, with a turnover frequency of 10.89 s −1 comparable to that of precious Pd-based catalysts, presented the highest selectivity to styrene (90.3%) at nearly 100% conversion of phenylacetylene in semibatch operation. This catalyst was further evaluated in a continuous fixed-bed reactor for semihydrogenation of a model C 8 aromatic fraction of pyrolysis gasoline (a mixture of phenylacetylene, styrene, ethylbenzene and xylene), which aimed at assessing its practical application of recovering styrene from pyrolysis gasoline. The results showed that at complete conversion of phenylacetylene, the styrene concentration in the product was always kept at a stable level and higher than its initial concentration over 100 h of time on stream, demonstrating high selectivity and good stability of NiZn 3 /AlSBA-15. Finally, the application of NiZn 3 /AlSBA-15 was extended to other phenylacetylene derivatives.
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
ACS Applied Nano Materials
·
2025
·
IF 5.5
Weijie Jia,Haifeng Wang,Chen Xue,Yaying Li,Qi Xiao
Selective hydrogenation of phenylacetylene is a crucial industrial reaction, yet developing catalysts with both high selectivity and activity remains challenging. Conventional hydrogenation catalysts often exhibit unevenly dispersed active metals, leading to agglomeration and reduced catalytic performance. Herein, with the aid of the ice-templating (ICT) strategy, we present TiO2-supported Pd nanocluster photocatalysts with ultralow Pd loading (0.1 wt %). The optimized Pd/TiO2–ICT catalyst achieves exceptional catalytic performance under ambient conditions (room temperature and atmospheric pressure) with methanol solvent and light irradiation, delivering 99% phenylacetylene conversion alongside 98% styrene selectivity. Advanced characterization reveals the catalyst’s superior structural features, including ultrasmall Pd clusters (1.2 nm diameter) and reduced Pd–Pd coordination number (6.3), which are significantly better than conventional counterparts. Systematic investigations establish a clear positive correlation between catalytic efficiency and critical structural parameters: smaller cluster dimensions and lower metal coordination numbers at equivalent Pd loadings. Mechanistic studies through comprehensive characterization elucidate that the photogenerated hydrogen radicals (•H) from methanol splitting directly drive the selective hydrogenation process. This study offers insights into both the application and structure–activity relationship of the ICT-based catalysts.
研究领域:
材料科学
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催化化学
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产品关联
DOI
高影响因子
ACS Applied Nano Materials
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2021
·
IF 5.097
Yang Liu,Wei Guo,Xiaojun Li,Peng Jiang,Ning Zhang,Minghui Liang
The selective hydrogenation of alkynes to alkenes is very important for both industry and scientific investigation, and overhydrogenation of alkynes to alkanes is the biggest problem to be solved. Suppressing the catalytic hydrogenation of alkenes to alkanes and keeping the efficient conversion from alkynes to alkenes at the same time is a viable solution, but the slight difference in structure between alkynes and the corresponding alkenes causes great difficulty in realizing such a target. The Pt/C–Cu bimetallic catalysts are used to catalyze the selective hydrogenation of phenylacetylene (PA) to styrene (ST). High-resolution STEM and EXAFS results show that the prepared Pt/C–Cu catalysts are composed of copper single atoms and Pt nanoparticles. In particular, Pt/C–Cu is a catalyst in which copper single atoms cover the surface of Pt nanoparticles. The experimental results reveal that the selectivity of ST strongly depends on the coverage of Cu single atoms over Pt nanoparticles in Pt/C–Cu, so selective hydrogenation of PA is a structure-sensitive reaction. The selectivity of ST can reach 94.4% at a PA conversion of 100% in the selective hydrogenation of PA over Pt/C–0.5Cu, an optimized Pt–Cu bimetallic catalyst; after selective removal of PA in ST from 100 to 30 ppm over the same catalyst, the yield of ST reaches 99.97%. The chemisorption results of H2 and probe molecule ethene (C2H4) over the Pt–Cu/C catalysts reveal that Cu single atoms covering on the surface of Pt nanoparticles weaken the Pt–H and Pt–C2H4 interactions, so the catalytic hydrogenation of the carbon–carbon double bond over Pt/C–0.5Cu can be tremendously suppressed. The added Cu single atoms over Pt nanoparticles are not poisonous sites because they can also act as the active centers to activate hydrogen and the carbon–carbon double bond.
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
INORGANIC CHEMISTRY
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2021
·
IF 5.165
Zhiyang Zhang,Gui Liu,Liping Ding,Mi Hu,Jing Gu,Wenlong Xu,Qingbo Xiao
The microenvironment surrounding the metal clusters on a carrier produces a tremendous influence on its catalytic performance. In this work, the promotion effect of the zeolitic inner host on catalytic performance of encapsulated platinum nanoclusters is reported. In the reaction of phenylacetylene semihydrogenation to styrene, Pt@X-zeolite, where platinum nanoclusters are encapsulated into the inner microporosity of the X-zeolite, exhibits an ∼3.37 times increased turnover frequency and a much better selectivity of 87.6% in comparison to the referenced Pt/X-zeolite of 79.3% selectivity to styrene at the same reaction conditions, in which the platinum nanoclusters are located at the exterior of the zeolite. Meanwhile, the Pt@X-zeolite displays a higher stability after 10 cycles of the reaction. Through the detailed characteristics, the excellent performance of Pt@X-zeolite is mainly due to the promotion of the zeolitic framework on the encapsulated Pt clusters, resulting in “electron-deficient” Pt clusters, leading to a stronger interaction with the π* molecular orbitals of phenylacetylene and thus enhancing the activation and conversion of phenylacetylene. The zeolite cavity wrapped with encapsulated Pt clusters regulates the adsorption trend of phenylacetylene through the acetylene group on it, promotes the desorption of styrene, and strengthens its selectivity. Meanwhile, Pt@X-zeolite has an excellent stability through the zeolite framework, which protects the Pt species from being lost. This investigation reveals the importance of the zeolitic microenvironment on the catalytic performance of encapsulated metal species and deepens the cognition for this type of catalyst.
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
Reaction Kinetics Mechanisms and Catalysis
·
2022
·Vol. 135
·期 5
·2533-2550
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IF 1.843
Chen Wei,Bao Zhichang,Zhou Zhiming
A series of non-precious bimetallic NiM x /SiO 2 (M = Zn or Co) catalysts with a fixed Ni loading of 5 wt% and different molar ratios of M/Ni (0.004–1.97) were prepared by glucose pyrolysis and applied to the selective hydrogenation of phenylacetylene. The properties of the catalysts were characterized by N 2 physisorption, CO chemisorption, ICP-OES, TGA, XRD, HRTEM, XPS, and DRIFTS. The activity and selectivity of the bimetallic catalysts could be tuned by varying the Zn/Ni and Co/Ni molar ratios, which were almost independent of the metal particle size (with a similar size of 4.1–5.5 nm), but predominantly determined by the geometric and/or electronic effects of the catalysts. Among all the catalysts studied, NiZn 0.05 /SiO 2 and NiCo 0.09 /SiO 2 presented higher selectivity to styrene (86.3% and 88.0%, respectively) at above 99% conversion of phenylacetylene. The high selectivity of the former was attributed to the geometric and electronic effects of the Ni–Zn alloy, while the latter was due to the geometric effect caused by the addition of Co. The activity and selectivity of NiCo 0.09 /SiO 2 were maintained during six consecutive cycles, indicating its good stability in the selective hydrogenation of phenylacetylene.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
·
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
·
催化材料科学
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产品关联
DOI
高影响因子
Materials
·
2024
·Vol. 17
·期 8
·1921
·
IF 3.1
Yu Wang,Tao Xing,Lifeng Yan
Hydrogen is a dangerous gas as it reacts very easily with oxygen and may explode; therefore, the accumulation of hydrogen in confined spaces is a safety hazard. Composites consisting of unsaturated polymers and catalysts are a common getter, where the commonly used polymer is 1,4- diphenylethynyl benzene (DEB). Silicone rubber (SR) is a good carrier for hydrogen-absorbing materials due to its excellent chemical stability and gas permeability. In this work, polysiloxane, water, and a emulsifier are ultrasonically injected into a uniform emulsion, and the hydrogen getter DEB-Pd/C (Palladium on carbon) is then added. Under the catalysis of platinum (Pt), the cross-linking agent undergoes a hydrosilylation reaction to cross-link polysiloxane in emulsion to form silicone rubber. Then, the water was removed by freeze-drying, and the loss of water constructed a porous frame structure for silicone rubber, thus obtaining porous silicone rubber. The difference in hydrogen absorption performance between porous silicone rubber and ordinary silicone rubber was compared. It was found that, with the increase in water in the emulsion, the porous frame of silicone rubber was gradually improved, and the hydrogen absorption performance was improved by 243.4% at the highest, almost reaching the theoretical saturated hydrogen absorption capacity. Porous silicone rubber was prepared by emulsion mixing, which provided a new idea for further improving the hydrogen absorption performance of silicone rubber.
研究领域:
材料科学
·
化学工程
✓ 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）