Catalysis Science & Technology
·
2015
·Vol. 6
·期 9
·3027-3037
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IF 5.426
Yanan Liu,Yufei He,Daran Zhou,Junting Feng,Dianqing Li
Aiming at the preparation of catalysts with well-controlled structures, bimetallic PdCu catalysts containing only small amounts of Pd were prepared by two different methods for partial hydrogenation of acetylene. The highly dispersed and stable PdCu catalyst with the Pd : Cu atomic ratio of 1 : 40 was obtained from a Pd(OH)2/CuMgAl hydrotalcite (HT) precursor by a modified co-precipitation method. The obtained PdCu catalyst possessed uniform PdCu nanoalloys with an average size of 1.8 ± 0.3 nm. As a comparison, the impregnation method was also employed to prepare bimetallic PdCu catalysts and it was confirmed that the Pd-rich(core)–Cu-rich(shell) structure was dominant. Under identical reaction conditions, approximately 100% conversion and 82% selectivity at 100 °C were achieved using the PdCu nanoalloy catalyst which were 23% and 12% higher than those of the Pd-rich(core)–Cu-rich(shell) catalyst. The preferable activity was ascribed to the homogeneous nanoalloy structure and small size effect. The enhanced selectivity was attributed to the strong synergistic effect of PdCu. More significantly, this superior catalytic performance can be retained after 48 h of continuous reaction due to the excellent resistibility against carbon deposition and the confinement effect.
研究领域:
催化化学
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材料科学
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有机合成
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DOI
高影响因子
ACS Materials Au
·
2022
·
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
·
纳米技术
✓ 已验证
DOI
ACS Sensors
·
2024
·
IF 8.2
Mingxue Zhang,Jihao Bai,Chengming Sui,Yilin Wang,Ziqi Liu,Tianrun Zheng,Fengmin Liu,Xishuang Liang,Geyu Lu
Hydrogen (H2) is colorless, odorless, and has a wide explosive concentration range (4–75 vol %), making rapid and accurate detection of hydrogen leaks essential. This paper demonstrates a method to modify the spatial distribution of nanocrystals (NCs) by adding surfactants to improve the sensing performance. In order to explore its potential for H2 gas-sensing applications, SnO2, containing different mass percentages of PdCu NCs, was dispersed. The results show that the 0.1 wt % PdCu-SnO2 sensor based on surfactant dispersion performs well, with a response to 0.1 vol % H2 that is 18 times higher than that of the undispersed 0.1 wt % PdCu-SnO2 sensor. The enhanced gas-sensing ability after dispersion can be attributed to the fact that the uniform distribution of NCs generates higher quantum efficiency and exposes more active sites on the carrier surface compared to nonuniform distribution. This study provides a simple, novel, and effective method to improve the sensor response.
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
ACS Applied Nano Materials
·
2024
·
IF 5.3
Ziqiang Wang,Yile Wang,Hugang Zhang,Hongjie Yu,You Xu,Kai Deng,Hongjing Wang,Liang Wang
Glycolic acid is used as a high-value-added chemical in a wide range of biological, chemical, and medical applications, and current large-scale production of glycolic acid usually suffers from harsh synthesis conditions and low selectivity. In this work, we report the coproduction of glycolic acid and hydrogen by electroreforming ethylene glycol using palladium–copper hydrides with hyperbranched nanocrystals (PdCu-H HNCs) as highly active electrocatalysts. The anodic ethylene glycol oxidation reaction (EGOR) requires only a low overpotential of 0.808 V at 100 mA cm–2. In a two-electrode system, PdCu-H HNCs show a low voltage of 0.824 V at 100 mA cm–2 for continuous production of glycolic acid and H2, with maximum Faraday efficiencies of 93% and nearly 100%, respectively. This work highlights the concurrent production of high-value glycolic acid and hydrogen with low energy consumption using palladium hydride-based electrocatalysts.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Cleaner Production
·
2023
·
IF 11.1
Lujie Zuo,Shufan Yu,Rongjun Zhang,Hongwei Li,Yu Wu,Rufat Abiev,Zhao Sun,Zhiqiang Sun
Methanol is a competitive candidate for in-situ hydrogen supply; however, the techniques of methanol-to-hydrogen production are suffered from high reforming temperatures and catalyst deactivation . In this work, the chemical looping oxidative reforming of methanol is conducted using a Pd–Cu-based catalytic oxygen carrier (PdO–CuO–CuMn 2 O 4 ). Synergistic enhancement of lattice oxygen induction and Pd–Cu alloy activation is confirmed, thereby achieving efficient methanol reforming at a temperature as low as 200 °C. Under such low temperatures, the hydrogen production rate can reach an average of 11.2 times higher than that of CuO/ZnO/Al 2 O 3 . Moreover, the catalytic oxygen carrier remains relatively satisfying redox durability after 30th cycle. SEM and AFM measurements reveal the high degree of roughness at the PdO–CuO–CuMn 2 O 4 surface, in which the methanol activation can be effectively promoted. XRD and XPS measurements verify the formation of Pd–Cu alloy, as proved by the charge transfer from Pd to Cu. During the redox looping, Pd–Cu alloy is formed and re-separated to be PdO and CuO, thus remaining homogenous distribution of the active phase on an atomic scale. Meanwhile, the lattice oxygen also plays a crucial role in methanol activation, synergistically enhancing the low-temperature reforming of methanol. This study provides a new implication for designing functionalized catalytic oxygen carrier materials , which will substantially promote in-situ hydrogen supply for proton exchange membrane fuel cells.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Chunhong Fu,Song Shu,Lin Hu,Zixun Liu,Zhouyang Yin,Xiaoshu Lv,Sen Zhang,Guangming Jiang
Selective electrocatalytic nitrate reduction reaction (NO 3 RR) to dinitrogen (N 2 ) is essential to nitrogen-cycle management and environmental sustainability. Palladium-based nanomaterials were extensively studied as NO 3 RR catalysts, but only delivered limited N 2 selectivity (<50%, NH 3 dominated the product). Here we report that, by tuning bimetallic composition of CuPd alloy nanowires, the Cu 28 Pd 72 nanowires deliver a near-unit conversion of NO 3 – -N and an unprecedented N 2 product selectivity of 75.9 ± 5.2% in treating 22.5 mg L −1 NO 3 – -N solution at −0.80 V vs. Ag/AgCl. Combining in-situ spectrometric measurements and theoretical calculations, we demonstrate that the contiguous Pd ensemble with a specific size at catalyst surface is essential to the N 2 formation via a kinetically-favored pathway of NO 2 * → NO* → N* → N 2 *. Alloying Pd with Cu is indispensable as Cu contributes to the N*-N* pairing by initiating the NO 3 – –NO 2 * conversion and lowering the H ads coverage on catalyst. This work discloses the key surface atomic structure for N 2 formation, and provides a guideline for the design of efficient NO 3 RR catalyst that enables selective NO 3 – –N 2 conversion.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Chenghu Zhang,Zezhou Xing,Ying Li,Tong Xu,Yinghui Sun,Jie Bai
Utilizing metal alloying strategies to fully exploit the role of precious metals in upgrading biomass chemicals remains both a challenging task and a key sustainable strategy. To improve the hydrogen transfer efficiency of furfural molecules in the catalytic transfer hydrogenation pathway, we report a Pd–Cu alloy composite nanocatalyst supported on mesoporous-structured zirconia through electrospinning technology. The chemical states of Pd and Cu in the catalyst were studied using XRD, HRTEM and XPS characterization methods, proving the presence of the PdCu alloy. A series of synthesized monometallic and bimetallic catalysts were tested for their ability to catalyze the catalytic transfer hydrogenation of furfural. Results showed that the PdCu alloy catalyst exhibited excellent performance similar to that of the monometallic Pd catalyst. 95.6% furfural conversion and 91.5% furfuryl alcohol selectivity were achieved at 170 °C and 2 MPa N2 for 12 h, and the catalytic activity did not decrease significantly after 6 cycles. The excellent catalytic activity was mainly attributed to the alloy and solvent effects, which promoted the improvement in hydrogen transfer efficiency.
研究领域:
化学工程
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催化材料
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生物质转化
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Tianxing Yang,Yuliang Feng,Rui Ma,Qiang Li,Hong Yan,Yanan Liu,Yufei He,Jeffrey T. Miller,Dianqing Li
In this work, a simple post-treatment has been carried out on a solid palladium–copper alloy to enhance the ethylene selectivity without any loss of activity. In all catalysts, PdCu/C catalysts post-treated at 375 °C exhibit improved ethylene selectivity (86%) compared to the solid PdCu/C catalysts (61%) at 100% acetylene conversion with comparable catalytic activity. During the post-treatment, the average size of PdCu nanoparticles is maintained at 6.6–6.8 nm, and no obvious segregation is observed. X-ray photoelectron spectroscopy and in situ extended X-ray absorption fine structure (EXAFS) results display that Pd is in a metallic state for all PdCu catalysts before and after post-treatment. Moreover, the EXAFS fitting results show that the Pd–Pd bond is gradually replaced by the Pd–Cu bond. The good separation of Pd atoms by Cu is also proven by XRD characterization, which shows that a body-centered cubic PdCu structure with uniform distribution of Pd and Cu in a unit cell forms under 375 °C post-treatment. The rearrangement of Pd and Cu atoms has a limited impact on the surface Pd dispersion, avoiding the activity loss due to the decrease in Pd sites. The improved selectivity could be attributed to the isolation of Pd and the accompanied d-band center downshifting, which favors the desorption of π-bonded ethylene species.
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
RSC Advances
·
2018
·Vol. 8
·期 61
·34853-34859
·
IF 2.936
Xingqiao Wu,Qingfeng Xu,Yucong Yan,Jingbo Huang,Xiao Li,Yi Jiang,Hui Zhang,Deren Yang
Pd@Pt core–shell nanocrystals with ultrathin Pt layers have received great attention as active and low Pt loading catalysts for oxygen reduction reaction (ORR). However, the reduction of Pd loading without compromising the catalytic performance is also highly desired since Pd is an expensive and scarce noble-metal. Here we report the epitaxial growth of ultrathin Pt shells on PdxCu truncated octahedra by a seed-mediated approach. The Pd/Cu atomic ratio (x) of the truncated octahedral seeds was tuned from 2, 1 to 0.5 by varying the feeding molar ratio of Pd to Cu precursors. When used as catalysts for ORR, these three PdxCu@Pt core–shell truncated octahedra exhibited substantially enhanced catalytic activities compared to commercial Pt/C. Specifically, Pd2Cu@Pt catalysts achieved the highest area-specific activity (0.46 mA cm−2) and mass activity (0.59 mA μgPt−1) at 0.9 V, which were 2.7 and 4.5 times higher than those of the commercial Pt/C. In addition, these PdxCu@Pt core–shell catalysts showed a similar durability with the commercial Pt/C after 10 000 cycles due to the dissolution of active Cu and Pd in the cores.
研究领域:
材料科学
·
电化学
·
催化反应
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Materials Chemistry Frontiers
·
2022
·Vol. 6
·期 16
·2190-2200
·
IF 8.683
Chengguang Liu,Xiaolei Guo,Zhen-Feng Huang,Jinheng Li,Li Gan,Lun Pan,Chengxiang Shi,Xiangwen Zhang,Guidong Yang,Ji-Jun Zou
Due to the utilization of renewable energy and proton sources, the electrochemical nitrogen reduction reaction is considered as an efficient, sustainable, and carbon-neutral route to replace the industrial Haber–Bosch process. However, restricted by the highly competitive hydrogen evolution reaction and the highly inert NN bond, electrochemical nitrogen reduction research still faces significant challenges with a low level of selectivity and activity. Herein, we demonstrate a catalyst (PdCu/TiO2−x) composed of oxygen vacancy-rich TiO2−x nanosheets and PdCu alloy nanoparticles by the co-reduction method of metal precursors. Such a catalyst exhibits excellent electrocatalytic performance at room temperature and pressure, with an NH3 yield rate of 8.51 mmol gcat−1 h−1 and the corresponding faradaic efficiency of 49.09% at −0.1 V vs. the reversible hydrogen electrode, which are much higher than most reported palladium-based catalysts and their alloy catalysts. Characterization and experimental results confirm that by properly constructing the surface defect and nanoalloy structure, the optimized electronic structure and synergistic effect can not only effectively improve the N2 adsorption and activation, but also reduce the reaction barrier, resulting in efficient electrocatalytic performance. Meanwhile, the introduction of Cu accelerates the hydrogen desorption, further effectively improving the faradaic efficiency. Overall, we explored the electrocatalytic performance and mechanism of the bimetal alloy catalyst, as well as the optimization strategies for enhancing the nitrogen mass transfer process, providing new insight into the rational design of a highly efficient e-NRR system through tuning of the catalyst and reaction environment.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
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
·
工业化学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
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
·
材料科学
✓ 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）