JOURNAL OF CATALYSIS
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2019
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IF 7.723
Xiaozhen Shi,Xin Wen,Shilin Nie,Jie Dong,Jingde Li,Yongqing Shi,Huiling Zhang,Guoyi Bai
Nickel is a highly active catalyst for the semi-hydrogenation of alkynes. However, the low selectivity of the alkene product caused by the over-hydrogenation reaction on Ni has hindered its practical applications. In this work, we report a new nickel nitride (Ni 3 N)-catalyzed semi-hydrogenation of alkynes to the corresponding alkenes. The Ni 3 N nanorods were facilely fabricated via a direct pyrolysis of the solid mixture of nickel acetate tetrahydrate and melamine (Mlm). The Ni 3 N phase in the optimum catalyst (Ni 3 N/NC-6/5-550) is shown to be effective and stable in the semi-hydrogenation of alkynes, with a high yield and good selectivity for alkenes ( Z / E ratios up to >99/1). Both terminal and internal alkynes bearing a broad scope of functional groups are readily converted into alkenes with good chemo- and stereoselectivity. Notably, it was found that the over-hydrogenation can be markedly suppressed even at high conversion of alkyne. Density functional theory (DFT) calculations reveal that the low interaction between the alkene product and the Ni 3 N might plays a critical role in the selectivity enhancement.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Xin Song,Fangjun Shao,Zijiang Zhao,Xiaonian Li,Zhongzhe Wei,Jianguo Wang
Precise regulation of reaction selectivity at high conversions is the key to non-terminated alkyne semi-hydrogenation. Herein, a support modification strategy was employed to incorporate trace amounts of Mg elements into alumina support. The modified support loaded Pd catalyst optimized the activity and selectivity of the non-terminated alkyne semi-hydrogenation reaction. The TEM and XRD characterization of the catalysts demonstrated the entry of Mg elements into the Al 2 O 3 lattice to achieve the modification of the support. For the 2-butyne-1-ol semi-hydrogenation reaction, the Pd 0.5 /Mg 1 @Al 2 O 3 catalyst showed 99 % conversion and 97 % selectivity of the cis product at hydrogen pressure of 0.1 MPa and 25 °C. The introduced Mg element changed the electronic structure of Pd nanoparticles in the catalyst. The precise regulation of the 2-butyne-1-ol semi-hydrogenation reaction was achieved by adjusting the ratio of Pd 0 to Pd 2+ using the synergistic effect of Pd 0 and Pd 2+ .
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
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
ACS Nano
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2025
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IF 16
Xiuling Guo,Chao Feng,Zihao Yang,Shingo Hasegawa,Ken Motokura,Yong Yang
Engineering the local coordination environment of single metal atoms is an effective strategy to improve their catalytic activity, selectivity, and stability. In this study, we develop an asymmetric Pd–Ag diatomic site on the surface of g-C3N4 for the selective electrocatalytic semihydrogenation of alkynes. The single Pd atom catalyst, which has a locally symmetric Pd coordination, was inactive for the semihydrogenation of phenylacetylene in a 1 M KOH and 1,4-dioxane solution at an applied potential of −1.3 V (vs RHE). In sharp contrast, doping Ag sites into single Pd atom catalyst to form paired Pd–Ag diatomic sites with asymmetric Pd coordination substantially enhanced the reaction, resulting in a high conversion (>98%) with exceptional time-independent selectivity to styrene under identical conditions. Characterization and theoretical calculations reveal that the introduction of a Ag site into single Pd atoms disrupts their symmetry coordination by forming Pd–Ag bonds with N2–Pd–Ag–N configuration, thereby modulating the electronic and geometric structures of Pd sites, which in turn benefits the adsorption and activation of substrate and lowers energy barrier for the rate-determining step of semihydrogenation, ultimately enhancing the electrocatalytic reaction. This work provides a facile and powerful strategy for the design of advanced catalysts by tuning the local coordination environment for selective catalysis.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-12
·
IF 17.694
Guo Yalin,Huang Yike,Zeng Bin,Han Bing,AKRI Mohcin,Shi Ming,Zhao Yue,Li Qinghe,Su Yang,Li Lin,Jiang Qike,Cui Yi-Tao,Li Lei,Li Rengui,Qiao Botao,Zhang Tao
Semi-hydrogenation of acetylene in excess ethylene is a key industrial process for ethylene purification. Supported Pd catalysts have attracted most attention due to their superior intrinsic activity but often suffer from low selectivity. Pd single-atom catalysts (SACs) are promising to significantly improve the selectivity, but the activity needs to be improved and the feasible preparation of Pd SACs remains a grand challenge. Here, we report a simple strategy to construct Pd 1 /TiO 2 SACs by selectively encapsulating the co-existed small amount of Pd nanoclusters/nanoparticles based on their different strong metal-support interaction (SMSI) occurrence conditions. In addition, photo-thermo catalysis has been applied to this process where a much-improved catalytic activity was obtained. Detailed characterization combined with DFT calculation suggests that photo-induced electrons transferred from TiO 2 to the adjacent Pd atoms facilitate the activation of acetylene. This work offers an opportunity to develop highly stable Pd SACs for efficient catalytic semi-hydrogenation process.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2018
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IF 3.141
Yuangong Zhang,Xin Wen,Yongqing Shi,Ru Yue,Libin Bai,Qingtao Liu,Xinwu Ba
Sulfur-containing polymer supported palladium nanoparticles (Pd/SPMB) were prepared by using the cross-linked poly(N,N′-methylene bis(acrylamide)) (SPMB) as the platform. The SPMB was synthesized via the reversible addition–fragmentation chain transfer (RAFT) polymerization, from which the sulfur inherently exists in the RAFT polymer due to the use of thiocarbonate as the chain transfer agent, and could be further utilized as a modifier of Pd nanoparticles. The Pd/SPMB showed size-dependent activity and selectivity in the semihydrogenation of alkynes to alkenes. The catalyst with an average Pd size of 5.3 nm was active in the semihydrogenation of both internal and terminal alkynes. Most of the surface of Pd NPs was covered (or poisoned) by sulfide and thiolate due to the moderate complexation strength between Pd NPs and SPMB, thus leading to the selectivity enhancement toward alkene. Furthermore, the catalyst was highly stable and can be reused 10 times without an appreciable loss in either activity or selectivity.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
ChemCatChem
·
2016
·Vol. 8
·期 6
·1111-1118
·
IF 4.724
Xinlin Li,Wei Zhang,Yansheng Liu,Rong Li
Graphical Magnetic personality : A new magnetic porous carbon derived from metal–organic framework is synthesized through the direct carbonization of ZIF-67 crystals and utilized as a support for Pd nanocatalysts. The catalysts are tested in the semihydrogenation of phenylacetylene under extremely mild conditions. A new magnetic porous carbon (MDPC) derived from metal–organic frameworks (MOFs) was synthesized successfully through the direct carbonization of ZIF-67 crystals and utilized as a support for Pd nanocatalysts. The prepared MDPC not only retains the original morphology of ZIF-67 crystals but also provides a high surface area and excellent magnetic properties. The designed catalysts (Pd-MDPC) were tested in the semihydrogenation of phenylacetylene under extremely mild conditions. The Pd nanoparticles are highly dispersed on the MDPC matrix without aggregation and exhibited an excellent catalytic activity and high selectivity toward olefins under mild conditions (25 °C, H 2 1 atm). The Pd-MDPC catalysts were further investigated in the semihydrogenation of several other terminal alkynes. Compared with most traditional carbon materials, such as activated carbon and carbon nanotubes, the MDPC possesses an admirable magnetism so that it could be separated magnetically from the reaction system. Our study indicates that MOF-derived porous carbon is a suitable support for noble-metal nanocatalysts and has promise in the field of nanocatalysis.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
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IF 3.9
Jie Han,Xin Wen,Hongchao Wang,Tianren Wang,Yuzhen Sun,Luis Ricardez-Sandoval,Guoyi Bai
Selective semi-hydrogenation of alkynes plays a pivotal role in the field of chemical production but still suffers from low selectivity and catalyst stability. Herein, an aminoclay-derived nickel catalyst was constructed by replacing part of Mg 2+ by Ni 2+ in the skeleton and coordinating Ni 2+ with aminopropyl groups via a self-assembly synthetic strategy. The introduction of Ni 2+ facilitated the exfoliation of lamellar structure, resulting in highly exposed and uniformly dispersed Ni nanoparticles. The optimal catalyst showed an excellent catalytic performance with 99.9 % conversion and 98.9 % regio- selectivity to alkene ( cis / trans = 94:6) in diphenylacetylene semi-hydrogenation. Experimental data and theoretical calculations validated that the aminopropyl groups on NiMg-AC improved the activity and selectivity to alkene by tuning the adsorption/desorption energies of substrate/product. Furthermore, this non-precious metal catalyst showed stable activity and selectivity during cyclic testing, thanks to the strong interaction between Ni and the aminopropyl groups. This "self-assembly" synthetic strategy provides valuable guidance for the preparation of aminoclay-derived Ni catalysts for selective semi-hydrogenation.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Zhao Wang,Hao Yuan,Jian Tao,Shu-Lin Liu,Ying Hong,Zhi-Yi Hu,Jian Zhang,Bao-Lian Su
Semihydrogenation plays a key role in industrial hydrorefining of light alkenes, with a market above 400 billion by 2027. The high cost of commercial palladium-based catalysts strongly calls for innovation but with great challenges. Herein, copper nanoparticles decorated with a minimized ppm of Pd are developed through a chemical plating process to integrate the catalytic advantages of copper and palladium for achieving maximized catalysis in the semihydrogenation of a fatal impurity of butadiene in alkene feedstocks. The developed Pd–Cu catalyst (i.e., 114 ppm of Pd in Pd0.0033Cu1/TiO2) exhibits an unprecedented catalytic performance superior to commercial Pd/Al2O3, with 100% butene selectivity above 90% of butadiene conversion over 130 h on stream at 90 °C. Further exploration reveals that the atomically dispersed Pd on Cu nanoparticles, obtained at ultralow ppm levels of Pd loading, induces a hidden but critical H2 trap, which concentrates H2 on the Pd site for further H2 dissociation that offers intermediate hydrogen atoms to the tandem butadiene semihydrogenation over the third layer of Cu atoms neighboring Pd through hydrogen spillover. Moreover, a threshold on Pd density was identified at Pd/Cu surficial atomic ratio of 1/138 (i.e., Pd0.0033Cu1/TiO2) for maximizing butadiene semihydrogenation performance, based on an extreme collaboration between Pd for H2 dissociation and Cu for butadiene hydrogenation. This work provides important guidance for developing noble metal-saving catalysts in industrial applications.
研究领域:
催化化学
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材料科学
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工业化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Nano Materials
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2020
·
IF 0
Jun Wang,Qing Kuang,Xiaofang Su,Xiaowen Lu,Leipeng Leng,Mingyang Zhang,Chunmu Guo,Tong Li,Qian Xu,Shuhui Sun,J. Hugh Horton,Wei Wu,Zhijun Li
Supported single-atom catalysts have become one of the most exciting frontiers in heterogeneous catalysis. The physicochemical properties of these materials are highly interesting; however, the generation of stable single atoms on solid supports is still challenging. Herein, we report an efficient and operationally simple postsynthesis method, consisting of spatial confining, freeze-drying, and reducing steps, for the construction of singly dispersed palladium atoms on SAPO-31 (Pd1/SAPO-31) with promising application prospects in the semihydrogenation of alkynes. A typical Pd–N–C single-atom catalyst derived from the ZIF-8-supported palladium complex was prepared and compared to Pd1/SAPO-31. The Pd1/SAPO-31 catalyst showed outstanding performance in the semihydrogenation of both phenylacetylene (85% selectivity at 99% conversion, 40 min) and 1-chloro-4-ethynylbenzene (95% selectivity at 99% conversion, 60 min). In addition, this single-atom palladium catalyst was highly active in triethoxysilane oxidation. Most importantly, this catalyst retained its atomic dispersion and catalytic activity after high-temperature thermal treatment in Ar at 700 °C. This study demonstrates how zeolites can be used to confine atomically dispersed metal species and tune the activity and stability of these materials to meet the needs of practical applications.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
INORGANIC CHEMISTRY
·
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
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Yanan Liu,Jiaying Zhao,Junting Feng,Yufei He,Yiyun Du,Dianqing Li
Environmental benign non-noble NiCu catalysts with well-distributed homogeneous nanoalloy structure was fabricated from layered double hydroxide for semi-hydrogenation of acetylene. Compared with monometallic Ni catalyst, the introduction of Cu enhanced ethene selectivity and decreased the deactivation rate in long-term reaction. Furthermore, to give a thorough understanding on structure dependent performance, conventional impregnation was also used to obtain bimetallic NiCu catalyst for comparison. Interestingly, imp-NiCu/MMO presented the mixture of monometallic Ni, Cu and bimetallic NiCu. Catalytic results indicated that 100% conversion was achieved at 160 °C with improved selectivity (>70%) over NiCu nanoalloy catalyst, while bimetallic NiCu catalyst with mixed structure showed both poor conversion (50%) and selectivity (65%). Enhanced activity was attributed to small particle size (3.2 nm) and high metal dispersion (31.4%). Improved selectivity and anti-coking ability were related to the alloying of Ni with Cu, which was conducive to isolate Ni atoms from one another confirmed by STEM-EDX and transfer electron from Cu to Ni certified by XPS. Additionally, superior performance was also found in semi-hydrogenations of hexyne, phenylacetylene, 1,2-diphenylethyne and ethyl phenylpropiolate over NiCu nanoalloy.
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
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