Catalysis Science & Technology
·
2023
·Vol. 14
·期 2
·334-342
·
IF 5
Zhou Yang,Ru Wang,Hongji Liu,Zhou Chen,Xiaoli Hu,Limin Sun,Weikun Lai,Yunyun Dong,Weiping Fang,Xiaodong Yi
Selective hydrogenation is a significantly important catalytic process in many industrial processes, where Pd-based catalysts are the most commonly used. Herein, the surface properties of γ-Al2O3 were modified by the layered flower-like architectures of alkaline MgO using a simple hydrothermal method. Then, a series of Pd/Al2O3–MgO catalysts were prepared by an incipient wetness impregnation method for the selective hydrogenation of isoprene. The results showed that the Pd/Al2O3–0.12MgO catalyst exhibited superior catalytic performance with a high activity (93%) and high selectivity (99%) for the semi-hydrogenation products. Systematic studies have demonstrated that the support effect plays an important role in dispersing and stabilizing palladium particles. The reasons for the improved catalytic performance were attributed to the high dispersion of Pd nanoparticles, the changed electronic structure of Pd, and the strong interaction between Pd nanoparticles and supports. This work opens a simple route to regulate the electronic properties of active metal sites via support modification for selective hydrogenation reactions.
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ACS Catalysis
·
2026
·
IF 13.6
Xiao Jing,Shen Meiqing,Shen Gurong,Li Xinhua,Jia Liwei,Wang Yilin,Li Wei,Gao Feng
Developing Pd-based catalysts for methane oxidation that combine low-temperature activity with strong water tolerance remains a major challenge for emission control applications. Herein, we introduce a high-entropy architecture into Co 3 O 4 -based spinel supports to regulate Pd-support interfacial interactions. The resulting high-entropy support (HE-Co-Sp) forms a hybridized and electronically delocalized Co–O–M (M = multiple cations) network, providing dynamic electron-buffering capability. This electronic framework promotes rapid replenishment of reactive oxygen species at Pd sites, thereby enhancing low-temperature methane oxidation activity. Concurrently, interfacial electronic coupling induces electron transfer from the support to Pd, as evidenced by XANES, EXAFS, and Pd 3d XPS measurements, leading to a moderated Pd electronic state and suppressed H 2 O adsorption. As a result, Pd/HE-Co-Sp exhibits markedly improved stability under wet methane oxidation under highly O 2 -rich conditions compared with Pd/θ-Al 2 O 3 , Pd/Co 3 O 4 , and Pd/MnCo 2 O 4 . These findings establish high-entropy-induced electronic delocalization as an effective strategy for designing water-tolerant methane oxidation catalysts.
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Molecular Catalysis
·
2023
·
IF 4.6
Yanzhao Gao,Xianglei Meng,Shiqi Huang,Hui Wu,Liantao Jiang,Yu Zhou,Yuting Song,Yanyan Diao
Gamma alumina is widely utilized for preparing the supported noble metal catalysts for the hydrogenation reaction. It is an effective strategy to improve the catalytic performance of catalysts via modifying gamma alumina with alkaline earth metal to regulate its surface acidity and electronic properties. Herein, Pd catalysts supported by Al 2 O 3 and Mg-modified Al 2 O 3 are synthesized via the wet impregnation method, and the effects of MgO doping on the structure, composition, and surface acidity of Pd/γ-Al 2 O 3 catalysts are investigated via X-ray diffraction patterns (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Temperature programmed desorption (TPD). The results show that Pd/MgO-Al 2 O 3 –2 (γ-Al 2 O 3 modified with 2 wt% Mg) has more metallic state palladium and weak acid sites and exhibits the best catalytic performance for the hydrogenation of perfluoro-4-methyl-2-pentene (D1). Density functional theory (DFT) calculations on Pd/Al 2 O 3 and Pd/MgO-Al 2 O 3 –2 catalysts are also performed to further explore the mechanism of D1 hydrogenation. The studies for Gibbs free energy of the potential reaction steps and intermediates reveal a complex process to generate the target product C 6 F 12 H 2 , and the rate-determining-step is the addition of the first hydrogen on the second carbon of perfluoro-4-methyl-2-pentene molecule.
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ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Ruifa Su,Qianqian Han,Cheng Xu,Junchen Ouyang,Fanchen Meng,Yingyu Zhou,Xinglong Zhang,Zhida Gu,Weina Zhang,Fengwei Huo,Suoying Zhang
Pd/C catalysts have been widely applied in the debenzylation process due to their excellent ability of hydrogenolysis. However, they have been suffering from the problems of agglomeration and loss of active components, which lead to decreased and unstable activity. Thus, it is still a challenge to achieve Pd/C catalysts with high activity and stability. Herein, we propose a strategy for preparing Pd/C catalysts on porous carbon hollow spheres by a microwave discharge method. Due to the high-temperature property and reducibility of microwave discharge, Pd precursors can be rapidly reduced, resulting in well-dispersed Pd nanoparticles with a small size on the carbon carrier. Besides, the matched mesopores in the carbon hollow spheres can anchor Pd nanoparticles and effectively reduce the agglomeration and loss of Pd nanoparticles during the catalytic reaction. As a result, the as-prepared Pd/mesoporous carbon hollow spheres exhibit high and stable activity in the debenzylation reaction.
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高影响因子
JOURNAL OF CONTROLLED RELEASE
·
2023
·
IF 10.8
Tiantian Liu,Zehang Zhou,Mengxing Zhang,Puxin Lang,Jing Li,Zhenmi Liu,Zhirong Zhang,Lin Li,Ling Zhang
The cuproptosis cell death pathway brings fresh opportunities for tumor therapy. However, efficient and targeted cuproptosis induction in tumors is still a challenge. Unfortunately, the well-known cuproptosis initiator, disulfiram and copper complex (DSF/Cu 2+ ), also increases PD-L1 level in tumors, which may diminish the final therapeutic outcome. In this study, DSF/Cu 2+ -loading MXene nanosheets are coated with PD-1 overexpressing T cell membrane to generate CuX-P system. CuX-P could recognize and stick to PD-L1 on tumor cells like a patch, which promotes the endocytosis of both CuX-P and PD-L1 by tumor cells. Following internalization and release of DSF/Cu 2+ in the cytoplasm, PD-L1 expression is upregulated. However, due to the presence of CuX-P in the tumor microenvironment , the then supplemented PD-L1 on tumor surface again binds CuX-P for internalization. This feedback loop keeps blocking and consuming the PD-L1 on tumor surface and promotes the enrichment of CuX-P in tumors to induce cuproptosis. After CuX-P treatment with laser irradiation, strong anti-tumor immune responses are stimulated in a mouse model with triple-negative breast cancer. Thus, this study develops a tumor-targeted biomimetic system that offers simultaneous cuproptosis killing, photothermal therapy (PTT) and immunotherapy in mice.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jun Zhang,Chunyuan Wang,Shiyu Lu,Shuyue Liu,Pingjuan Liang,Huan Yi,Mengjie Li,Meng Jin,Rong Wang,Guangming Jiang
Enhancing the enrichment behavior of low-concentration chlorinated organic pollutants remains a significant challenge in electrocatalytic hydrodechlorination (EHDC) technology. Metal-loaded hollow nanoarchitecture has emerged as a promising nanoreactor to improve reaction enrichment behavior because of its tailorable microenvironments and electronic properties. Herein, a structural engineering strategy is developed to synthesize yolk-shell structured TiN spheres supported Pd nanoreactors (Pd/YS-TiN) with confined mesoscopic spaces. Characterization by multiple techniques reveals that the yolk-shell structure of YS-TiN, with high specific surface area (139.0 m 2 /g) and appropriately mesoporosity (6.9 nm), exposes numerous Pd nanoparticles (∼4.0 nm) on outer/inner surface of the shell and yolk-core solid sphere, ensuring an efficient utilization of active sites for enhancing the 2,4-DCP detoxification. Consequently, the structurally optimized Pd/YS-TiN nanoreactor consistently displays maximum reaction kinetics, dechlorination degree, faradaic current density, H* utilization and product selectivity, surpassing hollow TiN-supported Pd and Pd/C catalysts. The super EHDC performance of 91.8 % 2,4-DCP conversion, a specific activity of 1.68 min −1 mol Pd −1 , and a mass activity of 6.06 min −1 g Pd −1 is obtained at −0.85 V and 180 min, outperforming most reported catalysts. Combining experimental and density functional theory results, the exceptional reaction enrichment behavior of Pd/YS-TiN originates from (1) alleviating the overstrong adsorption of product phenol through strong metal-support interactions and (2) enhancing mass transport efficiency facilitated by the local concentration gradient and mesoporous shell. This study elucidates how metal-support interactions and mass transport synergistically enhance reaction enrichment behavior, showcasing potential benefits in environmental remediation applications.
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Molecular Catalysis
·
2021
·
IF 5.062
Huafan Li,Tiantian She,Guofeng Chen,Menghua Sun,Libo Niu,Guoyi Bai
In this paper, a stable Pd/NH 2 -SBA-15 catalyst was prepared by an ammonia evaporation method using amino-functionalized SBA-15 as support. Pd/NH 2 -SBA-15 showed excellent catalytic performance in the selective hydrogenation of phenol to produce cyclohexanone. Furthermore, this Pd/NH 2 -SBA-15 catalyst kept the conversion of phenol and selectivity of cyclohexanone both over 90 % even after 10 runs, much better than Pd/SBA-15 and the previously reported Pd-based catalysts, demonstrating the benefit of amine functionalization on the activity of supported Pd nanoparticles. TEM and XPS results indicate that small Pd particles were highly dispersed on the NH 2 -SBA-15 support and a stronger interaction occurred between the active Pd particles and the amine functionalized SBA-15 support, which could effectively inhibit the agglomeration of the active Pd particles during the reaction and then improve the stability of this catalyst.
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ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Jianguo Liu,Nan Wang,Jianan Liu,Ming Li,Ying Xu,Chenguang Wang,Yanzhi Wang,Haoquan Zheng,Longlong Ma
Highly selective catalytic hydrogenation of alkynes to alkenes is a highly important reaction owing to its industrial and commercial application. Specifically, semihydrogenation of terminal alkynes has been more challenging than internal alkenes even using Lindlar catalysts. Also, the high reduction degree state metal-supported catalysts like Pd0/C, Pt0/C, and Ru0/C have been well-known to be used widely in hydrogenation due to their super activity. However, charcoal can absorb a large amount of water; Pd/C with 50% water is convenient on a large-scale synthesis. Charcoal generally bears oxygen groups on its surface, which are responsible for low selectivity and undesired products. Even typically, only 10–60% of the Pd metal atoms are exposed, they still suffer from poor stability in acids owing to leaching. Herein, we intend to design active and stable metal catalysts with features as the following to avoid leaching: having strong interaction with the support and coordinatively unsaturated metal sites or low valence state metals physically isolated from the acid environment. Herein, a highly efficient semihydrogenation of terminal alkynes to produce alkenes has been realized using a heterogeneous Pd(II)/POP-GIEC catalyst, imine-linked, crystalline, and porous organic polymer supporter modified by coordination of Pd(OAc)2 to its walls under mild conditions. Surprisingly, for the first time, modified POP-supported low reduction degree PdII catalysts were synthesized efficiently, and they were successfully used in semihydrogenation of terminal alkynes. The substrate scope was studied and included both unfunctionalized as well as functionalized substituents on the para, ortho, and meta position of aromatic alkynes. The substrate having a substituent with the functionality of fluoro protected at the meta position was semihydrogenated with a high alkyne conversion of 100% and olefin selectivity (up to 99%).
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GREEN CHEMISTRY
·
2020
·Vol. 22
·期 13
·4341-4349
·
IF 9.48
Yuxue Xiao,Qingwei Meng,Xiaoli Pan,Chao Zhang,Zaihui Fu,Changzhi Li
para-Xylene (PX) is a basic building block of polyethylene terephthalate, which is currently produced from petroleum resources. Developing a renewable route to PX is highly desirable to address both economic and environmental concerns. Several attempts used noble metal catalysts, e.g. Pd/Al2O3, to synthesize PX from biomass-derived 4-methyl-3-cyclohexene-1-carboxaldehyde (4-MCHCA), but suffered from a severe decarbonylation reaction, resulting in toluene as the main product. In this paper, we report an FeOx modification strategy to suppress the decarbonylation reaction on a Pd/Al2O3 catalyst, leading to a drastic shift in selectivity towards PX with a yield up to 81% via a cascade dehydroaromatization–hydrodeoxygenation (DHA–HDO) pathway. Characterization and control experiments revealed that the electron density of Pd sites decreased in an FeOx-modified Pd/Al2O3 catalyst compared to Pd/Al2O3, thus tuning the preferential adsorption mode of the substrate from η2-(C,O), the key transition state of the decarbonylation reaction, to the η1-(O) mode that favors the hydrodeoxygenation process. Notably, this designed catalyst is highly stable and is readily applicable in the selective synthesis of a broad range of desired aromatic chemicals via the same DHA–HDO pathway from cyclohex-3-enecarbaldehyde derivatives. Overall, this work develops a controllable catalyst modification strategy that tailors an efficient catalyst for petroleum-independent bio-PX synthesis.
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2020
·
IF 3.807
Cong Luo,Jianghua Yang,Jinling Li,Shijie He,Bowen Meng,Tao Shao,Qiankun Zhang,Dongxia Zhang,Xibin Zhou
A strategy for the synthesis of Au@N-CQDs@Pd three-layer core-shell nanoparticles without the use of any surfactant is proposed in this work. Herein, N-doped carbon quantum dots (N-CQDs) are used as the reducing agent, stabilizing agent, and shape-directing agent. The morphology and structure of the final product were characterized by Transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and X-ray powder diffraction (XRD). The electrocatalytic test indicates the as-synthesized Au@N-CQDs@Pd 20 exhibites excellent activity for methanol oxidation in alkaline media, which is approximately 6 times higher than commercial Pd/C. And its resistance to CO and stability are also greatly improved. This work provides a simple and straightforward approach to prepare bimetallic core-shell electrocatalyst by using CQDs with high catalytic activity for alkaline fuel cells .
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CHEMICAL ENGINEERING SCIENCE
·
2020
·
IF 3.871
Yongwan Gu,Yunyan Li,Jiaoxia Zhang,Huiying Zhang,Chunhua Wu,Jing Lin,Juying Zhou,Yuhang Fan,Vignesh Murugadoss,Zhanhu Guo
Pd/C catalysts were prepared by an incipient-wetness impregnation and their catalytic performance in disproportionation of rosin was investigated. The texture structure, groups on the activated carbon surfaces, and acidity were characterized by N 2 physisorption-desorption, Fourier transform infrared spectroscopy (FTIR), and temperature-programmed desorption (TPD). The Pd/AC3 (treated at 443 K) had the highest Pd dispersion (23.60%) with the highest specific surface area of activated carbon (1057 m 2 /g). Nevertheless, the Pd/AC0 (original carbon black) had the lowest Pd dispersion (13.07%) with a lower specific surface area of original activated carbon (994 m 2 /g). Pd/AC3 presented a considerable catalytic activity in the rosin disproportionation reaction, with 64.15% dehydroabietic acid and without abietic acid in product. However, Pd/AC0 (Pd supported on the original carbon) showed a much lower catalytic activity in the rosin disproportionation reaction, with 42.64% dehydroabietic acid and 3.59% abietic acid in product.
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JOURNAL OF MATERIALS SCIENCE
·
2020
·Vol. 55
·期 24
·10482-10491
·
IF 3.553
She Tiantian,Niu Libo,Nie Shilin,Li Huafan,Qiao Xianliang,Ma Yuanyuan,Han Xue,Chen Guofeng,Bai Guoyi
A novel sodium alginate-based Pd-3D double network hydrogel Pd/Ca–Alg–PAAS has been fabricated and successfully applied in the selective hydrogenation of phenol for the first time. The prepared catalyst showed excellent catalytic activity and high selectivity (99.8%) for cyclohexanone in the selective hydrogenation of phenol. Furthermore, this double network hydrogel of Pd/Ca–Alg–PAAS still kept a conversion of over 80% with the selectivity for cyclohexanone being over 99% after 6 runs, superior to the single network hydrogel of Pd/Ca–Alg. TEM and FT-IR results demonstrated that the Pd species were highly dispersed in Pd/Ca–Alg–PAAS, and the addition of sodium polyacrylate could enhance the interaction between hydrogel and Pd 2+ and thus inhibit the agglomeration and loss of the active Pd species, accounting for the good stability of Pd/Ca–Alg–PAAS.
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