Catalysis Science & Technology
·
2015
·Vol. 6
·期 9
·3027-3037
·
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
·
材料科学
·
有机合成
✓ 已验证
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
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
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
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
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
ChemistrySelect
·
2024
·Vol. 9
·期 31
·e202400459
·
IF 1.9
Yongyu Huang,Xinxin Xia,Pei Li,Yaqian Gu,Hua Song,Cuiqin Li,Feng Li
Graphical Hydrogenation of furfural to furfuryl alcohol under H 2 and N 2 atmosphere are studied over PdCu/ZrPO with metal and Lewis acid sites. The PdCu metal active sites of PdCu/ZrPO involve both direct hydrogenation and transfer hydrogenation activities, and the Zr 4+ −O 2− Lewis acid-basic pairs of ZrPO have transfer hydrogenation activity. Hydrogenation of furfural to furfuryl alcohol under H 2 and N 2 atmosphere was studied over zirconium phosphonate (ZrPO)-supported PdCu (PdCu/ZrPO) catalysts. The direct hydrogenation and transfer hydrogenation activities of PdCu metal active sites and the transfer hydrogenation activity of Zr 4+ −O 2− Lewis acid-basic sites were investigated, respectively. The size and the distribution of Cu particles could be adjusted by altering the P/Zr molar ratio. Bimetallic PdCu could enhance the acidity of the PdCu/ZrPO catalysts, and improve the ratio of Lewis/Brønsted acid, which led to an increase in the transfer hydrogenation activity of Lewis acid-basic pairs. The electronic effect between Pd and Cu promoted furfural to absorb onto electron-deficient Cu through η1(O)-aldehyde configuration, which contributed to the direct hydrogenation and the transfer hydrogenation at metal active sites. Especially, the adsorption and dissociation of H 2 in electron-rich Pd were promoted, which significantly improved the direct hydrogenation activity.
研究领域:
催化化学
·
能源化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Lijun Yue,Wanjun Zhao,Jinfang Li,Ruifang Wu,Yongzhao Wang,Hongxi Zhang,Yongxiang Zhao
The impact of Indium (In) doping upon the catalytic performance of Pd-Cu/Al 2 O 3 for carbon monoxide preferential oxidation (CO-PROX) in hydrogen (H 2 ) rich atmosphere at low temperature has been studied. A series of catalysts with extremely low palladium (Pd) loading (0.06 wt%) are synthesized by the facile co-impregnation method. When the In/copper (Cu) atomic ratio equals 0.25, Pd-Cu-In 0.25 /Al 2 O 3 can keep 40% CO conversion and 100% carbon dioxide (CO 2 ) selectivity at least 120 min at 30 °C, which is significantly superior to the catalytic performance of Pd-Cu/Al 2 O 3 . The elaborate characterization findings reveal that the added In species to Pd-Cu/Al 2 O 3 causes Indium oxide (In 2 O 3 ) to generate, which produces the interaction of In 2 O 3 with Pd-Cu/Al 2 O 3 , further promoting the dispersion of copper chloride hydroxide (Cu 2 Cl(OH) 3 ). Moreover, the modification of In facilitates the re-oxidation of Pd 0 to Pd + through reducing the formation of palladium hydride (PdH x ) during the CO-PROX reaction. Meanwhile, the addition of In leads to the decrease of Cu + electron cloud density, making it easier to be oxidized to Cu 2+ . Collectively, the easy re-oxidation of Pd 0 and Cu + is favorable to fulfill the Wacker cycle between Pd and Cu species, thus improving the catalytic performance for CO-PROX.
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
ACS Catalysis
·
2021
·
IF 13.084
Yiwen Yang,Haifeng Qi,Huixiang Li,Zhanwei Xu,Xiumei Liu,Shuyin Yu,Zongchao Conrad Zhang
Efficient hydrolysis of β-1,4-glycosidic bonds of cellulose is a pivotal step in biorefineries of cellulosic biomass. In this work, we discovered that paired PdCl2–CuCl exhibited excellent synergetic catalytic activity over the single PdCl2 or CuCl in the hydrolysis of β-1,4-glycosidic bonds in 1-butyl-3-methylimidazolium chloride ([BMim]Cl) and further investigated the catalytic species in this system. The catalytic activity increased and reached a plateau at a CuCl/PdCl2 ratio of 1 with increasing molar ratio of CuCl/PdCl2 while keeping the Pd concentration constant. A combination of experimental evidence based on in situ far-infrared absorption, X-ray absorption, X-ray photoelectron, and electron paramagnetic resonance spectroscopies and DFT calculations demonstrate the coupling reaction between [PdIICl4]2– and [CuICl3]2– via the Cl bridge to form the heterometallic complex anion [Cl2PdII–Cl–CuICl2]2–. The heterometallic species is stable during the reaction and maintains its catalytic performance in the presence of various oxygenate additives. Using paired PdCl2–CuCl as a catalyst, the activation energy of hydrolytic cleavage of β-1,4-glycosidic bonds of cellobiose is determined as low as 95.8 kJ/mol. PdCl2–CuCl/[BMim]Cl combined with CrCl3 can be reused five times in cellobiose conversion to 5-hydroxymethylfurfural (5-HMF) without an apparent decrease of catalytic activity. The performance of this catalytic system is further verified for efficient cellulose conversion. More than 60% product yield is obtained at 100 °C from the cellulose, affording monosaccharides for efficient production of high value-added chemicals, such as 5-HMF, when CrCl3 is present to catalyze the conversion of glucose to 5-HMF.
研究领域:
生物化学
·
催化化学
·
生物质能
✓ 已验证
产品关联
DOI
高影响因子
Surfaces and Interfaces
·
2024
·
IF 5.7
Xusheng Yang,Le Zhou,Changsong Chen,Weidong Jiang,Xiaobin Zhang,Pingchuan Pan,Shengbin Zhou,Kaiming Zhang,Bin Xu
Novel magneto-thermo dual responsive organic-inorganic hybrid materials (PdCu/Fe 3 O 4 @SiO 2 @PNIPAM) were successfully prepared under γ-ray irradiation in this work. The γ-ray irradiation simultaneously induced the grafting of the polymer PNIPAM, and the in-situ anchoring of metallic Pd and Cu via an irradiation reduction. The catalytic performance of the prepared PdCu/Fe 3 O 4 @SiO 2 @PNIPAM hybrid material ( abbr . PdCu/FSP) was investigated for the dehydrogenation of ammonia borane (AB) and the tandem hydrogenation of halonitrobenzenes. The results showed that the as-prepared PdCu/FSP exhibited more excellent catalytic performance in the tandem hydrogenation reaction of halonitrobenzenes in comparison with a controlled sample by a traditional preparation method. Furthermore, the PdCu/FSP catalyst prepared at a radiation dose of 25 kGy achieved excess 99 % yield of m-chloroaniline (m-CAN) at room temperature within 5 min. The PdCu/FSP hybrid material could be easily recycled by simple magnetic separation, and increasing temperature led to obvious time-shortening behavior for facile magnetic separation. Owing to lack of the intrinsic drawbacks of conventional chemical reductants and radical initiators, the gamma-ray irradiation method provides an available strategy for the construction of hybrid catalytic materials towards the hydrogenated reduction of halonitrobenzenes.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2020
·
IF 6.215
Na Ye,Zhao Jiang,Tao Fang
Direct methanol fuel cells (DMFCs) have attracted extensive attention due to clean, efficient characteristics and portable applications. In this work, a series of Pd x Cu y /reduced graphene oxide (rGO) catalysts are assembled and the catalytic performances are investigated for methanol oxidation reaction (MOR) in alkaline media. The intrinsic surface electronic structures of the Pd x Cu y /rGO bimetallic catalysts are also studied to clarify the reaction mechanism. The results reveal that Pd 1.2 Cu 0.2 /rGO exhibits superior catalytic activity (1101.58 A g Pd −1 ), 4.2 and 5.2 times higher than those of the commercial PtRu/C and Pd/C catalysts. CO stripping suggests that the onset potential for CO oxidation on the Pd 1.2 Cu 0.2 /rGO catalyst is lower than those on the commercial PtRu/C and Pd/C catalysts, implying that the anti-CO poisoning ability is enhanced. Combined with the analysis of X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and Raman, the enhanced catalytic activity and anti-CO poisoning ability are attributed to the charge transfer and lattice compression between Pd and Cu, which modify the d-band center and weaken the adsorption of CO. Furthermore, a volcano plot is found between the MOR activity and d-band center, indicating that the excellent MOR activity is attributed to the optimal d-band center with the moderate adsorption strength of CO-like intermediates.
研究领域:
材料科学
·
电化学
·
催化反应
✓ 已验证
DOI
高影响因子
Nature Catalysis
·
2022
·Vol. 5
·期 6
·564-570
·
IF 40.706
Xie Yi,Ou Pengfei,Wang Xue,Xu Zhanyou,Li Yuguang C.,Wang Ziyun,Huang Jianan Erick,Wicks Joshua,McCallum Christopher,Wang Ning,Wang Yuhang,Chen Tianxiang,Lo Benedict T. W.,Sinton David,Yu Jimmy C.,Wang Ying,Sargent Edward H.
Renewable electricity-powered CO 2 reduction to multi-carbon (C 2+ ) products offers a promising route to realization of low-carbon-footprint fuels and chemicals. However, a major fraction of input CO 2 (>85%) is consumed by the electrolyte through reactions with hydroxide to form carbonate/bicarbonate in both alkaline and neutral reactors. Acidic conditions offer a solution to overcoming this limitation, but also promote the hydrogen evolution reaction. Here we report a design strategy that suppresses hydrogen evolution reaction activity by maximizing the co-adsorption of CO and CO 2 on Cu-based catalysts to weaken H* binding. Using density functional theory studies, we found Pd–Cu promising for selective C 2+ production over C 1 , with the lowest ∆ G OCCOH* and ∆ G OCCOH* - ∆ G CHO* . We synthesized Pd–Cu catalysts and report a crossover-free system (liquid product crossover <0.05%) with a Faradaic efficiency of 89 ± 4% for CO 2 to C 2+ at 500 mA cm −2 , simultaneous with single-pass CO 2 utilization of 60 ± 2% to C 2+ .
研究领域:
化学工程
·
电化学
·
可再生能源
·
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）