DALTON TRANSACTIONS
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2024
·Vol. 53
·期 9
·4048-4053
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IF 3.5
Lin Gao,Guoqiang Ding,Lei Zhu,Zhanqiu Yu,Hongju Li,Guoqiang Li,Yulei Zhu,Hongwei Xiang,Xiaodong Wen,Yong Yang,Yongwang Li
The dimethyl maleate hydrogenation activity of Cu, ZnO-X and physically mixed Cu+ZnO-X samples was systematically investigated to probe the essential role of ZnO in ester hydrogenation processes. Cu samples exhibited high CC bond hydrogenation ability with dimethyl succinate as the main product. Comparatively, ZnO was inactive in hydrogenation due to its weak ability to dissociate hydrogen while the CO group could be activated and adsorbed on the ZnO surface. Interestingly, physical mixing with ZnO significantly improved the CO hydrogenation activity of Cu samples. The H2-TPD results reveal the origin of “Cu–ZnO synergy”: hydrogen atoms formed on the copper surface can spill over to the ZnO surface and react with the adsorbed CO group.
研究领域:
催化化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Xiaojing Cui,Yequn Liu,Wenjun Yan,Yanfeng Xue,Yangang Mei,Jiamei Li,Xiaoqing Gao,He Zhang,Shanhui Zhu,Yulan Niu,Tiansheng Deng
Suppressing reverse water-gas-shift (RWGS) reaction is high desirable but challenging and underdeveloped for Cu/ZnO catalysts, particularly for commercial Cu/ZnO/Al 2 O 3 catalysts. Different from the current methodologies to reduce RWGS reaction, we report a simply surface silylation method for efficiently minimizing RWGS reaction over a commercial Cu/ZnO/Al 2 O 3 catalyst. This method suppresses STY CO (Space-time yield) from 97.4 to 0.7 g CO ·kg cat −1 ·h −1 , improving STY MeOH from 20.2 to 39.9 g MeOH ·kg cat −1 ·h −1 and methanol selectivity from 15.1 to 92.9 mol%. The combination of characterization methods and density functional theory calculations provide insight into the suppressing mechanism of surface silylation on catalyst. A hydroxyl (on ZnO)-promoted RWGS reaction cycle is discovered, which can be efficiently inhibited by the consuming of hydroxyls via surface silyation. Our results provide a way to regulate RWGS reaction on Cu/ZnO-based catalysts and are expected to the further use of silylation strategy to tune the interconversion of CO and CO 2 via RWGS/WGS reaction on hydrogenation catalysts.
研究领域:
催化化学
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材料科学
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理论计算化学
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产品关联
DOI
高影响因子
CATALYSIS LETTERS
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2023
·
IF 2.8
Fang Yu,Chen Fengtao,Qin Xianan,Zhang Bingying,Mei Xueting,Lu Wangyang,Li Nan
As one of extensively used photocatalysts, zinc oxide nanoparticles (ZnO NPs) can generate free radicals under proper light irradiation, thereby achieving excellent antibacterial performance. However, the requirement of using light activation has limited its application to wider fields. In addition, nano-copper (Cu NPs) have gradually attracted the attention of researchers due to their excellent antibacterial properties. However, the high surface activity of nanoparticles makes them easy to agglomerate, and Cu NPs are easily oxidized, which affect the antibacterial activity. By synthesizing Cu–ZnO composite nanoparticles and loading the particles onto low melting-point polyethylene terephthalate (LMPET) fibers, we have developed a novel catalytic fiber (Cu–ZnO@LMPET) that can generate active species without needing light. It was found that Cu–ZnO@LMPET fibers with the copper content of 5 wt% (vs. ZnO NPs) or above could achieve 99% antibacterial effects on S. aureus and E. coli under dark conditions. Moreover, the antibacterial rates against E. coli and S. aureus could still be larger than 97 and 98%, respectively, even if the fibers were washed 50 times. In-vitro biocompatibility assessment also displayed that the as-prepared fibers had superb cytocompatibility. These results indicate that our developed fibers have highly efficient antibacterial properties, good washing resistance and high stability. Thus, our work has shed new light on the use of Cu–ZnO NPs for antibacterial purposes.
Graphical Abstract
研究领域:
材料科学
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微生物学
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生物医学工程
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2023
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IF 8.6
Shubin Cheng,Qian Lei,Coner Deng,Weixin Lei,Honglin Chen
A green protocol for refining industrial chemicals containing formaldehyde (FA) impurities is presented here for the first time. FA, as an unreactant or a byproduct, causes separation problems in many industrial processes. It can be removed to a level of less than 1 ppm with easily separable methanol formation using commercial Cu/ZnO/Al 2 O 3 catalyst at atmospheric pressure in the absence of external hydrogen. The formation of methanol is achieved by the transfer of hydrogen species generated with the assistance of water to free FA, affording high methanol selectivity (62 %). By investigating potential intermediates and implementing deuterium labeling experiments, together with carbon and hydrogen balance calculations, a plausible pathway of water-assisted FA removal is proposed. Moreover, the in situ generated hydrogen species can be transferred directly into unsaturated compounds for selective reduction.
研究领域:
化学工程
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催化
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环境化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
·
IF 22.1
Ziyang Chen,Jinjun Wen,Yu Zeng,Mengyuan Li,Yukun Tian,Fan Yang,Molly Meng-Jung Li,Peirong Chen,Haomin Huang,Daiqi Ye,Limin Chen
Cu/ZnO-based catalysts have been extensively and intensively studied for CO 2 hydrogenation to methanol due to their relatively superior catalytic performance. However, the mediocre methanol selectivity over Cu/ZnO-based catalysts has not been disclosed mainly because the predominant by-product CO formation activity fails to arouse any attention, significantly deterring the further catalyst optimization. The ZnOx-Cu nanoparticles (NP)-ZnO interface, derived from strong metal-support interactions (SMSI), has been recognized to be more active for methanol formation compared with the classical direct contact Cu-ZnO interface. In order to disclose the origin of the mediocre methanol selectivity, these two types of Cu-ZnO interfaces have been designed and constructed through carefully manipulating the synthesis and heat pre-treatment conditions of the powder model catalysts. Then, methanol and CO formation behaviors over these two interfaces have been explored thoroughly in actual reaction conditions. Finally, the origin of the mediocre methanol selectivity over Cu/ZnO-based catalysts has been proposed. This work provides unique insights for designing efficient Cu/ZnO-based catalysts with high methanol selectivity and yield and puts forward an effective strategy to investigate the catalytic behaviors over different interfaces in actual reaction conditions.
研究领域:
催化化学
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能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2017
·
IF 4.339
Xinlei Wang,Kui Ma,Lihong Guo,Ye Tian,Qingpeng Cheng,Xueqin Bai,Jingjing Huang,Tong Ding,Xingang Li
Herein, we reduced the ZnO-modified copper phyllosilicate to synthesize a series of Cu/ZnO/SiO 2 catalysts ( x CuZn/SiO 2 ) which were mixed with γ-Al 2 O 3 for dimethyl ether steam reforming (DME SR). The structure and the formation of copper phyllosilicate were systematically characterized by nitrogen adsorption, XRD and IR. The novel synthetic route led to the remarkably high dispersion of copper species and adjustable Cu 0 /Cu + ratio on the catalyst surface, resulting in the superior catalytic performance for DME SR. The amount of Cu 0 and Cu + sites on the catalyst surface was dramatically affected by ZnO loading, and the turnover frequency results indicated that the 4CuZn/SiO 2 catalyst (Cu/Zn = 4) with the Cu 0 /Cu + ratio of 1 showed the highest catalytic performance. The XPS, H 2 -TPR and TEM results revealed the existence of strong interaction between Cu species and ZnO on the reduced 4CuZn/SiO 2 catalyst, which suppressed the reverse water-gas reaction and prevented the sintering of copper.
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
Yong Liu,Xinghua Zhang,Lungang Chen,Jianguo Liu,Qi Zhang,Longlong Ma
This study explores the efficacy of a cost-effective Cu-ZnO-Al 2 O 3 catalyst for one-pot hydrodeoxygenation of guaiacol into hydrocarbons. Notably, complete conversion of guaiacol was achieved, yielding a 99.6% hydrocarbon over the robust Cu(6)Zn(3)Al(1) catalyst under the conditions of 4 MPa H 2 , 300 °C, and 8 h with a catalyst/guaiacol ratio of 0.5 g/1.0 g. In-depth catalyst characterizations unveiled the presence of oxygen vacancies within the ZnO surface layer, acting as pivotal active sites that facilitated the hydrodeoxygenation of guaiacol. Furthermore, Density Functional Theory (DFT) calculations were employed to evaluate several potential active sites, revealing that the oxygen vacancy of ZnO on the Cu surface played a crucial role. This vacancy enhanced the adsorption of intermediate cyclohexanol and markedly reduced the energy barrier for the rate-limiting step. This comprehensive investigation sheds light on the catalytic pathway and offers insights into designing efficient and sustainable biofuel production processes.
研究领域:
催化
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化学工程
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材料科学
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能源
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2014
·Vol. 3
·期 2
·600-607
·
IF 0
Hanxing Chen,Ming Wen,Zaidi Huang,Qingsheng Wu,Jiali Liu,Teng Tu
Highly active Cu@ZnO brush-like nanostructures have been successfully synthesized through the heteroepitaxial growth process of ZnO branched nanorods (NRs) based on Cu core nanowires (NWs), and used for the evaluation of selective catalytic degradation for polycyclic aromatic compounds. The resultant Cu@ZnO nanobrushes, with the main diameter of ∼500 nm, consist of Cu core NWs with diameter of ∼50 nm and outer ZnO branch NRs shells with thickness of ∼250 nm. The as-designed Cu@ZnO nanobrushes exhibit high performance for the selective catalytic degradation of polycyclic aromatic compounds. Nearly 90% conversion with the reaction rate constant (k) of 0.012 min−1 can be achieved for anthracene, while only about 50% and 10% conversions are shown for phenanthrene and naphthalene, respectively. Besides the highly efficient transportation of electrons, Cu NWs have strong capacity for oxygen activation which results in the gathering of negative charges and rich chemisorbed oxygen onto the surface, which is responsible for the high catalytic efficiency of Cu@ZnO nanobrushes toward the selective degradation of anthracene.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Guiming Xie,Xingyang Bai,Yi Man,Pengju Ren,Rongrong Jin,Runduo Zhang,Kostya (Ken) Ostrikov,Zhou-jun Wang,Qingyuan Yang
Innovative catalyst design and in-depth mechanism understanding are imperative for industrialization of CO 2 hydrogenation to methanol. Herein, Al-doped Cu/ZnO catalysts, Cu/Al-ZnO-x (x = 1/32, 1/16 and 1/8, denoting Al/Zn molar ratio), were creatively synthesized using MIL-53(Al) as Al sources and reactive templates. The Cu/Al-ZnO-1/16 catalyst exhibited the highest methanol production rate among the Cu/Al-ZnO-x catalysts, which was 1.93 times as active as the conventional Cu/Al-ZnO-1/16-C catalyst using Al(NO 3 ) 3 ·9H 2 O as Al source. Structural characterizations reveal that the use of MIL-53(Al) led to higher S BET , more uniform Al distribution, more abundant oxygen vacancies, more appropriate metal-support interactions and larger amount of medium basic sites. Mechanism studies demonstrate that Al doping would markedly induce oxygen vacancy formation on Cu-ZnO interfaces and thus significantly boost methanol synthesis activity. This work offers a facile approach to develop efficient methanol synthesis catalysts and provides new insights into the nature of Al promotion in Cu/ZnO-based 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
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2019
·
IF 8.355
Chunlei Huang,Jinjun Wen,Yuhai Sun,Mingyuan Zhang,Yunfeng Bao,Yudong Zhang,Long Liang,Mingli Fu,Junliang Wu,Daiqi Ye,Limin Chen
ZnO plate, dominantly exposed polar high energy (0 0 0 1) plane, was used to load Cu to build Cu/ZnO plate model catalyst. The catalyst was reduced in different atmospheres and then evaluated for CO 2 hydrogenation to methanol. X-ray diffraction, scanning electron microscopy, quasi in situ X-ray photoemission spectroscopy, in situ UV-Raman, and CO 2 temperature programmed desorption characterizations have been carried out. The exploration results indicate that in situ tuning Cu nanoparticle (NP) morphology can be realized through varying reducing atmospheres. H 2 reduction induced the formation of small irregular spherical Cu NPs covered with large amount of migrated Zn, prompting CO 2 conversion and methanol synthesis . However, CO reduction induced the generation of ellipsoidal Cu NPs with medium size and low amount of migrated Zn, leading to poor catalytic performance for CO 2 hydrogenation. CO 2 hydrogenation to methanol displays apparent Cu NP morphology dependency over the Cu-ZnO based catalysts.
研究领域:
化学工程
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材料科学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Fanjing Wei,Xiaoxia Zhang,Junjie Liao,Jiawei Guo,Weiren Bao,Liping Chang
The reactive adsorption desulfurization mechanism of thiophene over Cu/ZnO sorbent in coke oven gas (COG) was established by a combination of theoretical and experimental study. The adsorption behavior of thiophene on Cu surface was studied by density functional theory (DFT) method. The C 4 hydrocarbons releases and sulfur migration over Cu/ZnO sorbent during the thiophene removal process were investigated by comparing with that over CuO, ZnO and CuO+ZnO (prepared by mechanical grinding of CuO and ZnO) sorbents. The results show that the parallel adsorption of thiophene on hexagonal closest packing (HCP) site of Cu (1 1 1) crystal face is the optimal adsorption mode. Cu 0 nanoparticles in Cu/ZnO sorbent have two important roles: (1) adsorb and dissociate H 2 , and (2) cleave the C–S bond of thiophene. The sulfur after the cleavage of C–S bond could transfer directly to ZnO and eventually be converted into ZnS without the intermediate product CuS. During thiophene removal, C 4 H 6 and C 4 H 10 are generated over Cu/ZnO sorbent in the presence of H 2 . ZnO in Cu/ZnO sorbent not only acts as an excellent sulfur accepter, but can greatly affect the adsorption properties by enhancing the spillover and storage of hydrogen atoms . Increasing the interaction between Cu 0 nanoparticles and ZnO to enhance hydrogen spillover is an effective way to improve the thiophene reactive adsorption activity of Cu/ZnO.
研究领域:
化学工程
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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
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Yegang Xia,Xingwen Cha,Xing Yan,Xueying Wang,Yanmei Cai,Kok Bing Tan,Jinxin He,Ting Qiu,Dongren Cai,Guowu Zhan
Regulation of abundant Cu-ZnO interfaces in Cu/ZnO catalysts is critical to the thermal hydrogenation of CO 2 to methanol. Herein, Cu-ZnO interfaces were precisely regulated by depositing thin ZnO films on copper phyllosilicates (CuSiO 3 ) through atomic layer deposition (ALD) to prepare Cu/ZnO/SiO 2 composite catalysts (denoted as x ZnO/CuSiO 3 , x is the number of ALD cycles) for CO 2 hydrogenation to methanol. Interestingly, 5ZnO/CuSiO 3 exhibited much higher methanol selectivity of 68.1 % and methanol space-time yield (STY MeOH ) of 0.39 g MeOH h −1 g cat −1 toward CO 2 hydrogenation at 275 ℃ and 3 MPa, as compared to the pristine CuSiO 3 (38.1 % and 0.24 g MeOH h −1 g cat −1 ), suggesting the significant role of Cu-ZnO interfaces. Compared to ZnO/CuSiO 3 (IM) prepared by the conventional impregnation method, 5ZnO/CuSiO 3 possessed much higher CO 2 conversion (13.8 % vs. 10.1 %) and methanol selectivity (68.1 % vs. 56.2 %). Furthermore, the catalytic activities of the prepared Cu/ZnO catalysts can be effectively regulated by changing the thickness of ZnO-ALD films, in which 5ZnO/CuSiO 3 showed the best catalytic activity. Various characterization methods were applied to demonstrate that ALD-ZnO was evenly laid flat on the surface of CuSiO 3 to construct abundant Cu-ZnO interfaces during the H 2 reduction treatment, which facilitated the dissociated activation of CO 2 and formation of CH 3 O* reaction intermediate and simultaneously inhibited the generation of CO byproduct. In addition, the density functional theory (DFT) calculations revealed the stronger interaction between Cu and ZnO over 5ZnO/CuSiO 3 , which implied more Cu-ZnO interfaces were generated for methanol production. Accordingly, this study verifies the significance of Cu-ZnO interfaces for CO 2 hydrogenation to methanol and provides a facile method to regulate Cu-ZnO interfaces by depositing ALD-ZnO films on the copper phyllosilicate precursor.
研究领域:
催化化学
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材料科学
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能源化学
✓ 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）