ACS Catalysis
·
2025
·
IF 13.1
Jia-qi Bai,Mei Ma,Huangfei Liu,Zhangkai Qian,Durui Liu,Yuncai Zhao,Yijing Gao,Jingshuai Chen,Mengdie Cai,Song Sun
The hydrogenation of nitriles is an environmentally friendly and atom-economical route to prepare high-value amines; however, it is still a challenge to control selectivity because of the occurrence of hydrogenation, self-coupling, and hydrogenolysis reactions during the hydrogenation process. It is highly desirable to develop efficient non-noble-metal catalysts for the hydrogenation of nitriles to secondary amines, although several noble metal catalysts have been reported. Herein, we successfully prepared a Cu–Ni/W20O58 catalyst and found that the Cu4.4–Ni0.6/W20O58 catalyst showed a 92.3% yield with initial TOFs of 270.0 h–1 at 373 K and 3 MPa H2 for the hydrogenation of benzonitrile (BN) to dibenzylamine (DBA), which was much superior to that of the monometallic Cu4.4/W20O58 and Ni0.6/W20O58 catalysts. Moreover, the Cu4.4–Ni0.6/W20O58 catalyst could be reused at least 4 times and was effective for the hydrogenation of various nitriles with superior selectivity to secondary amines. Furthermore, the reaction mechanism of BN hydrogenation for the Cu–Ni alloy of Cu4.4–Ni0.6/W20O58 was proposed on the basis of spectroscopic studies such as XRD, TPR, TEM, XAFS, and XPS, kinetic studies such as the effect of BN concentration and H2 pressure, the isotopic effect of hydrogen, and the effect of the reaction temperature and DFT calculations. The rate-determining step was the hydrogenation of benzylidenamine (BI) to the half-hydrogenated intermediate by one H atom over the Cu4.4–Ni0.6/W20O58 catalyst. The Ni–W20O58 interface was responsible for the adsorption and activation of BN, and the electron-rich Cu acted as the site for H2 dissociation; the synergistic effect of Cu and Ni led to the superior catalytic performance of the Cu4.4–Ni0.6/W20O58 catalyst.
研究领域:
催化化学
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材料科学
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环境化学
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产品关联
DOI
高影响因子
AICHE JOURNAL
·
2021
·Vol. 67
·期 10
·e17368
·
IF 3.993
Yu-Xia Li,Meng-Meng Jin,Shu Shi,Shi-Chao Qi,Xiao-Qin Liu,Lin-Bing Sun
Cu + -containing materials have great potentials in various applications like adsorptive desulfurization. Nevertheless, their applications are severely obstructed by poor stability of Cu + in air. Here, we first clarify the mechanism of Cu + oxidation by first-principle calculations and demonstrate that moisture accelerates Cu + oxidation dramatically. Then, the microenvironment of Cu 2 O-modified HKUST-1, a typical metal-organic framework, is adjusted from hydrophilic to hydrophobic with polydimethylsiloxane coating (producing Cu 2 O@HK@P). This isolates moisture from pores and enhances the stability of Cu + significantly even under oxygen atmosphere. Cu + in Cu 2 O@HK@P preserves well after exposed to air for 6 months, while Cu 2 O@HK lose almost all Cu + for 2 weeks. The optimal Cu 2 O@HK@P can remove 540 μmol g −1 of thiophene from hydrous fuel, which is much superior to Cu 2 O@HK (227 μmol g −1 ) and most reported adsorbents. Our strategy can also be applied to stabilize Cu + in various materials including zeolite, mesoporous silica, and activated carbon.
研究领域:
材料科学
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催化
·
能源化学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2017
·
IF 3.359
Guangfei Qu,Qian Zhao,Ronglong Jian,Junya Wang,Dianxin Liu,Ping Ning
Beginning with the formation of the ionic liquid/water two-liquid phase catalytic system for absorption of PH 3 , we designed and synthesized Cu + -[Bmim]PF 6 , which has a hydrophobic property, and later formed a two-liquid phase system with Cu + -[Bmim]PF 6 and water, which has high PH 3 absorption efficiency, and an effective separation of the product and the catalyst was achieved. The effects of temperature and O 2 concentration on phosphine absorption, and the distribution of catalytic components and products in the ionic liquid/aqueous two-phase system were studied. Moreover, the mechanism of Cu + -ILs/water two-liquid phase catalytic oxidation of phosphine was discussed based on results from the analysis of FT-IR and ion chromatography . The results demonstrated that the optimum oxygen content in the reaction was 3%, and the optimum reaction temperature was 45 °C. Cu + -ILs/water two-liquid phase system has a high absorption efficiency for PH 3 , the absorption process is liquid phase catalytic oxidation and the product is H 3 PO 4 . The two-liquid phase system is semi-intelligent. The system can achieve high performance liquid phase catalytic oxidation of PH 3 , as well as automatic separation of H 3 PO 4 .
研究领域:
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2014
·Vol. 111
·期 2
·633-645
·
IF 0.983
Yue Chuan-Jun,Gu Li-Ping,Su Yang,Zhu Shao-Ping
Cu/MgO and MgO nested on the surface of Raney Cu were prepared by a wet-mixing method and used as catalyst for glycerol hydrogenolysis. The texture of Raney Cu/MgO was characterized by X-ray diffraction and transmission electron microscopy, Brunauer–Emmett–Teller, and CO 2 -temperature-programmed desorption techniques. Results indicated that MgO was well dispersed in the pores of Raney Cu. Moreover, Raney Cu with large specific surface area had a larger contact surface for MgO, and a new phase of Cu–MgO was produced. Glycerol hydrogenolysis was selectively catalyzed under the synergistic effect of Cu and MgO in Cu/MgO catalyst. Under the moderate conditions of 180 °C and 1 MPa H 2 , the conversion of glycerol was 36.2 wt% and the selectivity for 1,2-propanediol was ~85 wt% when chemical equilibrium.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Haolan Liu,Zhili Chang,Jie Fu,Zhaoyin Hou
Cu-based catalysts play pivotal role in many industrial processes, however, its application under high temperature is restricted due to the low Tammann temperature of Cu. Improving the stability and activity of Cu-based catalysts at high temperature is a challenge. In this work, a stable Cu/ZnO@SiO 2 catalyst was prepared, in which silicon was introduced into CuZn-BTC precursor via a steam-assisted hydrolysis method before calcination and reduction. Characterizations found that Cu/ZnO@SiO 2 catalyst prepared via above strategy possesses increased surface area, more exposed active sites and excellent stability for ethanol dehydrogenation than Cu/ZnO (prepared from CuZn-BTC without SiO 2 ). It was confirmed that the space-time yield of acetaldehyde reached 9.0 g-acetaldehyde/g-cat/h, and Cu/ZnO@SiO 2 could maintain its activity within 200 h at 350 °C due to the ZnO decorated Cu particles (Cu/ZnO) were encapsulated in the octahedral shaped SiO 2 hollow.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMOSPHERE
·
2016
·
IF 3.698
Ying Han,Zhong-lin Chen,Ji-min Shen,Ji-he Wang,Wei-wei Li,Jun Li,Bin-yuan Wang,Li-na Tong
The role of Cu(II) in the reduction of N -nitrosodimethylamine (NDMA) with zero-valent metals was investigated by determining the effects of Cu(II) on the removal, kinetics, products, and mechanism. NDMA removal was enhanced, and all reactions followed a pseudo-first-order kinetic model except for the Fe and Fe/0.1 mM Cu(II) systems. The iron mass-normalized pseudo-first-order rate constants ( k MFe ) increased with the Cu(II) concentration. The zinc mass-normalized pseudo-first-order rate constants ( k MZn ) were identical to those with the Cu(II) concentrations from 0.1 mM to 1.0 mM and were higher with 2.0 mM Cu(II). The types of products detected were unchanged. Some unknown products were also found. NDMA was reduced to 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine , UDMH). Then, UDMH was reduced into dimethylamine (DMA) by the Fe/Cu(II) and Zn/Cu(II) systems. Catalytic hydrogenation was proposed as the reduction mechanism. Several copper species, such as Cu(OH) 2 in the Fe/Cu(II) system and Cu 2 O and Cu(OH) 2 in the Zn/Cu(II) system enhanced NDMA reduction. Differences between the Fe/Cu(II) and Zn/Cu(II) systems were caused by the reduction potentials and surface conditions of the different metals and the copper species in the various systems.
研究领域:
环境化学
·
水处理
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催化
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2023
·Vol. 30
·期 14
·40534-40550
·
IF 5.8
Fang Lei,Wu Guojian,Yao Keyu,Zhang Dongyang,Zhou Yongchao
A novel heterogeneous catalyst named MoS 2 /MIL-53(Fe, Cu) (MMFC) was prepared by hydrothermal method and applied in a heterogeneous electro-Fenton (hetero-EF) system for lomefloxacin (LOM) degradation in this work. Under the optimal conditions of current density 3 mA/cm 2 , catalyst dosage 0.100 g/L, and initial pH 6, 93.5% LOM (2 mg/L) removal efficiency was achieved in the MMFC hetero-EF system within 60 min, indicating an obvious improvement compared with the MIL-53(Fe, Cu) hetero-EF system. The good catalytic activity was attributed to more effective active sites of the catalyst and the conversion of Fe(II)/Fe(III) and Cu(I)/Cu(II) promoted by Mo(IV) in MoS 2 , which could be inferred by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) characterizations. The reusability and stability of MMFC were explored based on five cyclic experiments, and the average degradation efficiency reached 73.9%. Furthermore, the hetero-EF system could achieve the total removal of moxifloxacin and tetracycline within 6 min and 40 min, respectively. Quenching experiments revealed that the hydroxyl radicals (·OH) were the main reactive radicals while superoxide radicals (·O 2 − ) and singlet oxygen ( 1 O 2 ) played a certain part in LOM degradation. Finally, the possible mechanism of the hetero-EF process and LOM degradation pathways were proposed, including substitution, elimination, and cleavage of ring structures. Accounting for good catalytic performance, low preparation cost, and satisfactory versatility, the MMFC exhibited good potential to work as a hetero-EF catalyst for wastewater treatment.
研究领域:
环境科学
·
化学工程
·
材料科学
·
废水处理
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2017
·
IF 3.615
Yong Zhang,Huiping Zhang,Ying Yan
A heterogeneous catalyst (Cu/ZSM-5) was prepared by a metal-organic chemical vapor deposition (MOCVD) method under nitrogen atmosphere using Cu(acac) 2 as the copper precursor, and further characterized by XRD , AAS , SEM, BET, H 2 -TPR and XPS as well as catalytic activity performance for the oxidation of toluene. N 2 adsorption data revealed that the samples (CVD-4) prepared by MOCVD with calcination at 500 °C for 4 h possessed higher surface areas than that (CVD-BC) not calcined. The results of XPS demonstrated that CVD-4 exhibited higher redox property and more surface oxygen species compared with CVD-BC and IM (Cu/ZSM-5 catalyst prepared by impregnation). In particular, the CVD-4 catalysts prepared by MOCVD with calcinations showed the highest catalytic activity for toluene oxidation with 90% conversion of toluene at 293 °C with the feed concentration of 1000 ppm and GHSV of 15,000 h −1 , which was lower than IM (310 °C). The results of a reaction durability test revealed that the Cu/ZSM-5 catalysts prepared by MOCVD possessed excellent durability for toluene oxidation for 63 h, while the conversion of toluene fell down from 90% to 60% after 48 h over IM catalyst.
研究领域:
环境科学
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催化化学
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产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2015
·Vol. 44
·期 35
·15645-15652
·
IF 4.197
Hanxing Chen,Teng Tu,Ming Wen,Qingsheng Wu
New Cu2O-on-Cu nanowires (NWs) are constructed to develop the visible-light-driven activity of photocatalysts via the facile self-assembly of Cu2O nanoparticles (NPs) on a Cu NW surface assisted by a structure director, followed in situ reduction. In the resultant Cu2O-on-Cu NWs, the Cu2O NPs, with a diameter of 10 nm, show good distribution on the 50 nm-sized Cu single-crystal NWs. Owing to the band-gap adjusting effect and high electron transportation, the coupling of narrow-band-gap semiconductor Cu2O and excellent conductor Cu can lead to the markedly enhanced high visible light photocatalytic activity of Cu2O-on-Cu NWs toward the degradation of dye pollutants including Rhodamine B (RhB), methyl orange (MO) and methyl blue (MB). The as-designed Cu2O-on-Cu heterostructured NWs exhibit higher performance for the catalytic degradation of dye compounds than pure Cu2O. Nearly 60%, 100%, and 85% conversion with reaction rate constants (k) of 0.0137, 0.0746 and 0.0599 min−1 can be achieved for the degradation of RhB, MO and MB, respectively. Besides the highly efficient transportation of electrons, Cu NWs have a strong capacity for oxygen activation, which results in the gathering of negative charges and rich chemisorbed oxygen onto the surface. This may be responsible for the high catalytic efficiency of the Cu2O-on-Cu NWs toward the degradation of organic pollutants.
研究领域:
材料科学
·
环境科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysts
·
2023
·Vol. 13
·期 7
·1038
·
IF 3.9
Jincheng Wu,Guoguo Liu,Qin Liu,Yajing Zhang,Fu Ding,Kangjun Wang
The hydrogenation of methyl formate to methanol is considered one of the most effective methods for recycling methyl formate products. We recently developed a highly efficient and cost-effective Cu-SiO2catalyst using the ammonia-evaporation (AE) method. The Cu-SiO2-AE catalyst demonstrated superior performance, achieving a methyl formate conversion of 94.2% and a methanol selectivity of 99.9% in the liquid product. The catalyst also displayed excellent stability over a durability test of 250 h. Compared to the commonly used Cu-Cr catalyst in the industry, the Cu-SiO2-AE catalyst exhibited higher conversion of methyl formate and methanol yield under the same reaction conditions. Characterization results revealed a significant presence of Si-OH groups in the Cu-SiO2-AE catalyst. These groups enhanced the hydrogen spillover effect and improved hydrogenation efficiency by preventing sintering during the reaction to stabilize the Cu species. The strategy employed in this study is applicable to the rational design of highly efficient catalysts for industrial applications.Keywords:Cu-SiO2catalyst;hydrogenation of methyl formate;methanol;catalyst stability
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
COLLOIDS AND SURFACES B-BIOINTERFACES
·
2019
·
IF 3.973
Lingyan Yang,Liliang Chen,Yi-Chun Chen,Lei Kang,Jiantao Yu,Yuhang Wang,Chengjia Lu,Tsutomu Mashimo,Akira Yoshiasa,Chia-Hua Lin
Immiscible bimetallic Ag–Cu system has been synthesized by the pulsed plasma in liquid method with a graph of one pulse duration. Herein, by combining X-ray power diffraction, K-edge X-ray absorption near edge structure and high-resolution transmission electron microscopy, our results indicate that homogeneously alloyed Ag–Cu nanoparticles (Ag–Cu NAs) have the average diameter about 2.1 nm, composed by 48.5 at% Ag and 51.5 at% Cu with chemical analysis and the estimated lattice parameter was 3.873 Å. The antibacterial property of Ag–Cu NAs was detected against E. coli and S. aureus strains according to the colony formed abilities of bacteria on agar plates covered with the nanoparticles. With very short incubation period, Ag–Cu NAs completely inhibited the E. coli and S. aureus growth at an ultralow concentration. The mechanism of antibacterial property of Ag–Cu NAs was performed by the inductively coupled plasma-atomic emission spectrometry and the plane wave pseudopotential method implemented in the CASTEP package based on the density functional theory. The Ag + dissolution is correlated with antibacterial activity for Ag–Cu NAs-assisted antibacterial treatment. These findings obtained revealed that our Ag–Cu NAs could be served as a containing material of numerous bacteria-free products in order to avoid their bacterial contamination.
研究领域:
材料科学
·
微生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano Research
·
2019
·Vol. 12
·期 5
·1187-1192
·
IF 8.515
Zhu Xiyue,Rong Hongpan,Zhang Xiaobin,Di Qiumei,Shang Huishan,Bai Bing,Liu Jiajia,Liu Jia,Xu Meng,Chen Wenxing,Zhang Jiatao
Control of surface structure at the atomic level can effectively tune catalytic properties of nanomaterials. Tuning surface strain is an effective strategy for enhancing catalytic activity; however, the correlation studies between the surface strain with catalytic performance are scant because such mechanistic studies require the precise control of surface strain on catalysts. In this work, a simple strategy of precisely tuning compressive surface strain of atomic-layer Cu 2 O on Cu@Ag (AL-Cu 2 O/Cu@Ag) nanoparticles (NPs) is demonstrated. The AL-Cu2O is synthesized by structure evolution of Cu@Ag core-shell nanoparticles, and the precise thickness-control of AL-Cu 2 O is achieved by tuning the molar ratio of Cu/Ag of the starting material. Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) and EELS elemental mapping characterization showed that the compressive surface strain of AL-Cu 2 O along the [111] and [200] directions can be precisely tuned from 6.5% to 1.6% and 6.6% to 4.7%, respectively, by changing the number of AL-Cu 2 O layer from 3 to 6. The as-prepared AL-Cu 2 O/Cu@Ag NPs exhibited excellent catalytic property in the synthesis of azobenzene from aniline, in which the strained 4-layers Cu 2 O (4.5% along the [111] direction, 6.1% along the [200] direction) exhibits the best catalytic performance. This work may be beneficial for the design and surface engineering of catalysts toward specific applications.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
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