ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Wen Li,Kuncan Wang,Guowu Zhan,Jiale Huang,Qingbiao Li
The chemical transformation of CO2 to value-added chemicals and fuels remains a daunting research challenge, requiring the development of more efficient catalysts. The present work offers highly active integrated nanocatalysts for CO2 hydrogenation to dimethyl ether (DME) through tandem catalysis, that is, Pd/ZnO converts CO2 to methanol, and bio-ZSM-5 further catalyzes methanol dehydration to DME. Notably, the hierarchically porous bio-ZSM-5 with high pore connectivity was prepared by using low-cost rice husk and luffa sponge as biotemplates. The formation of bio-ZSM-5 involved three consecutive steps, including (i) diffusion of precursor species, (ii) confined crystal growth, and (iii) calcination treatment to remove the residual biomass. Interestingly, the obtained bio-ZSM-5 possesses abundant hierarchical porosity, including the intrinsic micropores from ZSM-5 frameworks, the mesopores from intracrystalline void space or pinholes in the intergrown zeolite layers, and the macroscopic channels from the original biomass architecture. It was found that the tetrapropylammonium hydroxide amount and Si/Al ratio were two critical factors affecting the crystallinity and porosity of the bio-ZSM-5. The silicon content in biomass (8.3 wt % in rice husk and 0.016 wt % in luffa sponge) also played a crucial role in the synthesis of bio-ZSM-5. Different spatial configurations of Pd/ZnO and bio-ZSM-5 significantly affected the DME yield, wherein spatial distances between the bio-ZSM-5 and Pd/ZnO components were adjusted by controlling the size of Pd/ZnO or the integration manners. The current results indicated that the closest proximity of the bifunctional catalyst was unfavorable for DME production (selectivity < 3%), because of which low-valent Zn cations from Pd/ZnO could displace the Brønsted acid sites on bio-ZSM-5 by ion exchange, and the powder mixing in the mortar was the best combination configuration of Pd/ZnO and bio-ZSM-5, promoting the CO2 conversion (10.8%) with a DME selectivity of 31% under the reaction of 300 °C and 30 bar. Furthermore, as compared to the traditional ZSM-5 based catalyst, the obtained Pd/ZnO/bio-ZSM-5 bifunctional catalysts showed excellent long-term stability in 60 h on stream with a less amount of coke formed in the spent catalysts.
研究领域:
催化化学
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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 ALLOYS AND COMPOUNDS
·
2020
·
IF 4.65
Kelin Hu,Feipeng Wang,Zijia Shen,Hongcheng Liu,Jianglin Xiong
In this paper, Pd/ZnO–SnO 2 hollow nanofibers prepared by electrospinning and magnetron sputtering . The sensing materials exhibited extraordinary hydrogen (H 2 ) sensing behavior – the response reached 171 at 270 °C, and besides, the response time and recovery time were as low as 19 s and less than 1 s at 240 °C, with steady high selectivity and good repeatability. Such an enhanced sensing performance could be attributed to the Pd/ZnO/SnO 2 ternary heterojunctions formed in the hollow nanofibers. Moreover, the materials were studied by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and especially the morphology formation process was further explained. The existence of Pd was confirmed to increase the resistance modulation range of heterojunction. In addition, the gas sensing mechanism based on the structure was proposed.
研究领域:
材料科学
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传感器技术
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纳米科技
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2015
·Vol. 7
·期 17
·7615-7623
·
IF 7.394
Lu Lin,Tong Zhang,Haiou Liu,Jieshan Qiu,Xiongfu Zhang
Controllable encapsulation of nanoparticles with metal organic frameworks (MOFs) has been an efficient way to impart the unique chemical and physical properties of the nanoparticles to metal organic frameworks and create new types of multifunctional MOF core–shell materials with enhanced properties. Here, a novel ZnO support-induced encapsulation strategy is reported to efficiently fabricate a Pd/ZnO@ZIF-8 core–shell catalyst, with Pd/ZnO as the core and ZIF-8 as the shell. The novel synthesis procedure involves first loading Pd nanoparticles onto the surface of the ZnO microsphere to form a Pd/ZnO core and then coating the core with a layer of defect-free ZIF-8 shell via ZnO-induced in situ ZIF-8 growth to obtain the Pd/ZnO@ZIF-8 core–shell catalyst. It was crucial that the ZIF-8 was in situ formed from the ZnO core in an ethanol solution only containing 2-methylimidazole under mild conditions. This strategy allowed for the growth of ZIF-8 right on the surface of Pd/ZnO via the reaction between ZnO and the 2-methylimidazole ligands, and thus avoided the random deposition of ZIF-8 crystals on the Pd/ZnO core as in the case of the conventional ZIF-8 synthesis solution. Furthermore, use of ethanol as the solvent also favored achievement of the well-defined Pd/ZnO@ZIF-8 structure, since the ethanol solution of 2-methylimidazole was able to keep the balance between ZnO dissolution and ZIF-8 formation. The as-prepared Pd/ZnO@ZIF-8 core–shell microsphere as an efficient catalyst displayed excellent performance in terms of size-selectivity, stability and anti-poisoning in the liquid hydrogenations of alkenes.
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
高影响因子
JACS Au
·
2022
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IF 0
Yuhai Sun,Junliang Wu,Yaolin Wang,Jingjing Li,Ni Wang,Jonathan Harding,Shengpeng Mo,Limin Chen,Peirong Chen,Mingli Fu,Daiqi Ye,Jun Huang,Xin Tu
Plasma-catalytic CO2 hydrogenation is a complex chemical process combining plasma-assisted gas-phase and surface reactions. Herein, we investigated CO2 hydrogenation over Pd/ZnO and ZnO in a tubular dielectric barrier discharge (DBD) reactor at ambient pressure. Compared to the CO2 hydrogenation using Plasma Only or Plasma + ZnO, placing Pd/ZnO in the DBD almost doubled the conversion of CO2 (36.7%) and CO yield (35.5%). The reaction pathways in the plasma-enhanced catalytic hydrogenation of CO2 were investigated by in situ Fourier transform infrared (FTIR) spectroscopy using a novel integrated in situ DBD/FTIR gas cell reactor, combined with online mass spectrometry (MS) analysis, kinetic analysis, and emission spectroscopic measurements. In plasma CO2 hydrogenation over Pd/ZnO, the hydrogenation of adsorbed surface CO2 on Pd/ZnO is the dominant reaction route for the enhanced CO2 conversion, which can be ascribed to the generation of a ZnOx overlay as a result of the strong metal–support interactions (SMSI) at the Pd–ZnO interface and the presence of abundant H species at the surface of Pd/ZnO; however, this important surface reaction can be limited in the Plasma + ZnO system due to a lack of active H species present on the ZnO surface and the absence of the SMSI. Instead, CO2 splitting to CO, both in the plasma gas phase and on the surface of ZnO, is believed to make an important contribution to the conversion of CO2 in the Plasma + ZnO system.
研究领域:
催化化学
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等离子体化学
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环境科学
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可持续能源
✓ 已验证
产品关联
DOI
PubMed
JOURNAL OF MATERIALS SCIENCE
·
2024
·Vol. 59
·期 45
·21027-21039
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IF 3.5
Zhang Peng,Guo Mengya,Wang Fujiang,Tang Qiong,Ge Hui,Guo Shuke,Zhou Ligong,Li Xuekuan,Dong Jinxiang,Tang Mingxing,Liu Lei
Selective hydrogenation is an effective approach to utilize coal tar and slurry oil to produce high value-added fine chemicals. However, how to efficiently improve the selectivity of the target product and the stability of the catalyst is difficult. Herein, the PdZn alloy catalyst was synthesized by the assistance of strong interaction between active metal (Pd) and support (ZnO) for hydrogenation of anthracene to symmetrical octahydro anthracene (sym-OHA). The PdZn alloy catalyst reduced at 400 °C was found to exhibit a 100% conversion of the anthracen with 84.77% selectivity to sym-OHA under the optimized conditions (200 °C, 1 MPa). The characterization analysis indicated that the PdZn alloy with electron-rich Pd active sites is more efficient in the selective hydrogenation than the pure Pd metal. The study of the deep hydrogenation of sym-OHA (Hydrogenation of sym-OHA to perhydroanhtracene) showed that PdZn alloy catalysts were inactive to further hydrogenation of sym-OHA. Additionally, due to the strong interaction between Pd and ZnO, the Pd/ZnO(400) catalyst shows high stability for five cycles. These findings are of practical significance for the selective hydrogenation of polycyclic aromatic hydrocarbons (PAHs) to produce high value-added products.
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
Catalysis Science & Technology
·
2021
·Vol. 11
·期 13
·4398-4405
·
IF 6.119
Liangcai Zhang,Xinyu Liu,Hengwei Wang,Lina Cao,Chenxi Huang,Shang Li,Xiaohui Zhang,Qiaoqiao Guan,Xiang Shao,Junling Lu
Strong metal–support interaction (SMSI) has long been studied in catalytic reactions. Proper utilization of the SMSI effect might not only improve the stability of the catalysts, but also the activity and selectivity. In this work, using the atomic layer deposition (ALD) technique, we synthesized a series of Pd/ZnO catalysts with Pd particle sizes ranging from 1.6 to 7.9 nm. Upon H2 reduction at elevated temperatures, these Pd/ZnO catalysts display a size-dependent SMSI effect wherein the larger-size Pd particles are more prone to be encapsulated by ZnO compared to the smaller ones. In the reaction of CO2 hydrogenation, we show that such size-dependent SMSI, together with the size-related CO binding strength on Pd particles, provides a higher activity and methanol selectivity to the Pd particles larger than ~2.5 nm.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2025
·
IF 7.7
Ertai Na,Binrong Chen,Xudong Liang,Jiayu Li,Ruiqin Gao,Xu Zou,Guo-Dong Li
n -Butanol, as a typical volatile organic compound, is widely used in the chemical, coating, and daily chemical industries. However, its volatility can lead to deteriorating air quality and health risks, necessitating the development of highly sensing and selective real-time detection sensors. This investigation proposes a synergistic sensitization strategy by modifying ZnO nanosheets with Pd nanoparticles to address the low response and poor selectivity of traditional ZnO semiconductor gas-sensing materials. Experimental results indicate that the 0.25 wt% Pd-ZnO exhibits a response value of 400 for 50 ppm of n -butanol, which is seven times that of pure ZnO, and the detection limit is as low as 0.1 ppm. Combined with density functional theory calculations, we reveal for the first time the synergistic sensing-enhancement mechanism at the Pd-ZnO interface: the Zn sites adsorb the oxygen atoms in n -butanol through bonding interactions, while the Pd nanoparticles can synergistically adsorb the hydrogen atoms in n -butanol, thereby enhancing the specific recognition capability towards n -butanol. This research provides new insights into the sensing enhancement mechanisms of noble metal-modified semiconductors, these insights may be widely applied in the design and synthesis of specific sensing materials, catalytic materials, and adsorption materials.
研究领域:
材料科学
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化学传感
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纳米技术
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表面化学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Xing Yan,Dongren Cai,Meihong Lin,Zhijie Wu,Yegang Xia,Yanmei Cai,Sajid Ali,Kok Bing Tan,Andriambinintsoa Ranaivoson Tojonirina,Hao Sun,Guowu Zhan
The selective hydrogenation of CO 2 to methanol demands precise control of both catalyst architecture and reaction pathways. Here, we design an atomic layer deposition (ALD)-engineered Pd/ZnO/ZrO 2 ternary catalyst with atomic-scale ZnO interlayers to decouple and reconfigure active sites at dual interfaces (Pd-ZnO and ZnO-ZrO 2 ). This interfacial engineering drives a 7-fold enhancement in methanol space–time yield (0.584 vs. 0.084 g MeOH g cat −1 h −1 ) and switches the dominant reaction pathway from CO-mediated to formate-driven selectivity (methanol selectivity remarkably surges from 6 % to 64 %). Multimodal characterization and theoretical calculations reveal that ZnO interlayers orchestrate bifunctional cooperation: activating CO 2 /CO adsorption while suppressing CO/CH 4 formation through electronic effects. Long-term stability study uncovers a dynamic restructuring mechanism, where Pd-ZnO interfaces gradually evolve into PdZn β alloy phases under the reaction conditions. This work establishes ALD-mediated interface design as a generalizable strategy to manipulate reaction networks and methanol selectivity in catalytic CO 2 hydrogenation systems.
研究领域:
催化化学
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材料科学
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化学工程
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可持续能源
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表面科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Yiming Chen,Chuan Wang,Yi Liu,Qianwen Zhang,Ling Zhou,Yi Zhang
The selectivity and stability of catalysts for methanol synthesis from CO 2 still remain to be enhanced. In this work, we synthesized a series of Pd/ZrO 2 catalysts inversely loaded with various metal oxide promoters (ZnO, In 2 O 3 , and CeO 2 ), those would partially cover Pd metal surface and form some new metal-promoter interface, to explore the nature in the performance of CO 2 hydrogenation to methanol. The catalyst synthesized by this approach could limit the growth of Pd particles during the reduction and form new metal–metal oxide interfaces with different functions of CO 2 hydrogenation, improving the reaction performance of Pd-ZrO 2 catalysts. As a result, the ZnO-Pd/ZrO 2 catalyst exhibited the highest CO 2 conversion (12.0 %), methanol selectivity (95.6 %), and STY of methanol (472 g MeOH kg cat -1 h −1 ), with excellent stability. The results of HRTEM, H 2 -TPR, XPS, and XAFS showed that the ZnO-Pd/ZrO 2 catalyst had the typical Pd-ZnO interface with Pd 2+ species after the H 2 reduction, which could enhance the adsorption and activation of CO 2 . In addition, the in situ DRIFTS and NAP-XPS results implied that the Pd-ZnO interface significantly improved the formation of formate (HCOO*) and methoxy (H 3 CO*) species, which were considered to be the key intermediates of methanol generation, and thus greatly enhanced the selectivity of methanol.
研究领域:
催化
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化学工程
·
材料科学
·
环境化学
✓ 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）