Catalysts
·
2023
·Vol. 13
·期 4
·673
·
IF 3.9
Jinghu Zhu,Hui Liu,Xueyan Zhou,Zhijun Wang,Liancheng Bing,Dezhi Han,Guangjian Wang,Fang Wang
Cu-based catalysts, modified by gallium addition via the stepwise co-precipitation method, were studied for the liquid phase hydrogenation of hydroxypivalaldehyde (HPA) to neopentyl glycol (NPG). Through physico-chemical techniques, the effects of gallium introduction on the Cu trimetallic catalyst performance and the reaction mechanism of HPA hydrogenation were discussed. The characterization results showed that gallium introduction can influence the dispersion, reduction, and distribution of active Cu species, as well as their reactivity. Herein, the catalyst with 2 wt% gallium addition exhibited excellent catalytic performance with HPA conversion rate and NPG selectivity of 93.5% and 95.5%, at a reaction pressure of 3 MPa, temperature of 110 °C, hydrogen-aldehyde ratio (molar ratio) 10:1, and liquid space-time at a speed of 8.4 h−1. The good performance could be attributed to gallium doping tending to dynamically tune the interaction between the components, increasing Cu dispersion and the distributions of Cu+and Cu0species on the catalyst surfaces.Keywords:HPA hydrogenation;NPG synthesis;Cu-based catalyst;gallium modification;Cu+/Cu0
研究领域:
化学工程
·
催化材料
✓ 已验证
产品关联
DOI
高影响因子
Arabian Journal of Chemistry
·
2022
·
IF 6.212
Lusheng Shi,Pengquan Yan,Zhihua Gao,Wei Huang
Due to the complexity of the structure–activity relationship of the CuAl 2 O 4 spinel catalyst, optimization of the catalyst structure is a great challenge. In this paper, three different CuAl 2 O 4 spinel catalysts were prepared by the solid-phase method using copper hydroxide, copper nitrate, and copper oxide as the copper source, respectively, to study the difference in the structure of CuAl 2 O 4 spinel catalysts induced by the raw materials and the catalytic behavior for CO hydrogenation. The structure of CuAl 2 O 4 spinel catalyst was characterized by XRD, BET, SEM, TEM, H 2 -TPR and XPS. The activity of CO hydrogenation over the CuAl 2 O 4 spinel catalyst without pre-reduction was evaluated in the slurry reactor. The results demonstrated that different copper sources had obvious influence on the CuAl 2 O 4 spinel texture properties, surface enrichment degree, as well as decomposition and reduction ability, which further regulated the ratio of Cu + /Cu 0 and thus affected the catalytic performance, especially the alcohol distribution. The CuAl 2 O 4 spinel, employing copper hydroxide as the copper source, showed better selectivity of C 2+ OH, which was assigned to a higher ratio of Cu + /Cu 0 , along with larger pore size and pore volume. Moreover, the synergistic effect between Cu 0 and γ-Al 2 O 3 improved the selectivity of dimethyl ether.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Nan Xi,Shiting Chen,Ruixi Bao,Qinglian Wang,Yixiong Lin,Jun Yue,Rong Wang,Chen Yang,Wang Yin,Ting Qiu
Furfuryl alcohol (FOL) is commercially available by selective hydrogenation of furfural (FAL). A variety of catalysts have been developed for such purpose, among which Cu-based catalysts show superior catalytic performance. However, copper nanoparticles with complex valence states are easy to agglomerate during hydrogenation reaction, which might have a negative influence on the catalytic performance. The carbon coating is an efficient strategy to prevent the sintering of Cu-based catalysts. Herein, a strategy based on the thermal decomposition of Cu-EDTA complex was designed to prepare carbon encapsulated Cu-based catalysts. The prepared catalysts were applied in the selective hydrogenation of FAL to FOL in the batch reactor. The results showed that a nearly quantitative conversion of FAL with a selectivity of 98.7 % towards FOL was achieved using CuO x @NC-150 (molar ratio of Cu: Na 4 EDTA·4H 2 O=2:1; obtained by oxidative activation at 150 °C) under 140 °C, 3 MPa in 4 h. The performance was comparable to that of the commercial CuCr 2 O 4 catalyst under the identical conditions. In addition, the developed carbon encapsulated Cu-based catalysts exhibited a slightly better stability than CuCr 2 O 4 catalyst in terms of FOL yield in five consecutive cycles. XPS and XAES characterizations implied that the presence of a suitable surface ratio of Cu + /(Cu + +Cu 0 ) of the prepared catalyst may contribute to the selective hydrogenation of FAL to FOL.
研究领域:
催化化学
·
绿色化学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Hui Wang,Wenru Zhao,Mooeez Ur Rehman,Wei Liu,Yuxi Xu,Huijiang Huang,Shengping Wang,Yujun Zhao,Donghai Mei,Xinbin Ma
In the utilization of renewable resources derived from biomass, hydrodeoxygenation (HDO) is one of the most critical steps in the bio-oil upgrading process. Herein, a series of copper phyllosilicate nanotube (CuPSNT) catalysts were successfully prepared and applied in the chemosynthesis of cyclohexane via the phenol HDO reaction. Against the presumption that mono-metal copper was not active for the complete hydrogenation of aromatic compounds, a cyclohexane yield of 97.8% at the total conversion of phenol was achieved at 230 °C on the CuPSNT catalysts with a Cu/Si ratio of 1:1. The kinetic analysis suggested that further conversion of cyclohexanol to cyclohexane is the rate-determining step in the phenol HDO. Cu0 accounts for the hydrogenation, while Cu+ is responsible for the adsorption of phenol and cyclohexanol and in charge of further cyclohexanol dehydration. This conclusion is further confirmed by density functional theory calculations. This work demonstrates that the synergy between Cu0 and Cu+ species of CuPSNT catalysts plays a critical role in the HDO process of phenol, and mono-metal Cu can accomplish both the saturation of aromatic rings and the removal of oxygen groups.
研究领域:
催化化学
·
可再生资源利用
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·
IF 15.7
Ren Yuqi,Cheng Miao,He Hongbin,You Changjun,Duan Lunbo,Sun Zhenkun,Peng Ruoxuan,Zhu Yuan-Hao,Zhang Hongyang,Zhou Jiancheng,Huang Kai,Guan Jie,Li Naixu
CO 2 -to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O 2 partial pressures and sluggish C 2 -product formation. Herein, Ru 0.6 Cu 1 (Cu 0 –Cu 1+ )/CeO 2 catalysts with adaptive O 2 tolerance are prepared by O 2 -mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H 2 O dissociation. Photothermal effect promotes O 2 -driven self-assembly of Cu 0 –Cu 1+ charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of * CHOCO intermediates and restructuring the C–C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C 1 to C 2 , as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g −1 C 2 H 4 with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency—25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Water Process Engineering
·
2022
·
IF 7.34
Peng Xu,Pengfei Zhu,Xin Liu,Zhuoyu Yang,Jingwei Ma,Qiulai He
Fe 2+ activated peroxodisulfate (Fe 2+ /PDS) system has been widely studied for its efficient degradation of pollutants. However, the slow circulation of Fe 3+ /Fe 2+ greatly restricted the application of the system. In the study, AOII was significantly degraded by using Fe 3+ coupled with Cu 0 activate PDS system (Fe 3+ /Cu 0 /PDS system). Compared with the traditional Fe 2+ /PDS system, the Fe 3+ /Cu 0 /PDS system greatly improved the degradation of AOII and the decolorization rate reached 80.6 % within 30 min. The quenching experiments and electron spin resonance (EPR) showed that both hydroxyl radical (•OH) and sulfate radical (SO 4 •− ) were the mainly primary reactive oxygen species in the Fe 3+ /Cu 0 /PDS system with the contribution rates of SO 4 •− and •OH being 60.54 % and 25.06 % respectively. In the Fe 3+ /Cu 0 /PDS system, Cu 0 formed Cu + through H + corrosion and PDS/O 2 oxidation . Then, Cu + oxidized by O 2 to produce H 2 O 2 and Fe 3+ was reduced by Cu 0 and Cu + to form Fe 2+ . Finally, Cu + and Fe 2+ catalyzed PDS to generate SO 4 •− , and •OH was yield by the process of Cu + and Fe 2+ induced H 2 O 2 and the reaction of OH − /H 2 O and SO 4 •− . Common water matrices such as NO 3 − and SO 4 2− had no effect on the degradation, while Cl − promoted the degradation, and CO 3 2− and fulvic acid inhibited the degradation of AOII. Over 68.5 % of AOII was degraded in the experimental water samples and the Fe 3+ /Cu 0 /PDS system had great degradation performances in practical water sample of other contaminants. Moreover, the final discharge of total dissolved copper was <1 mg/L after sediment and filtering.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
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
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Zhao Yang,Yong Liu,Jianlong Wang
Zero-valent copper (ZVC) has shown potential as an oxygen activator for the degradation of organic pollutants from aqueous solution. Nevertheless, the high leaching of copper ions and the demand for acidic condition limited its application. In this study, a novel mesoporous carbon hybrid loaded zero-valent copper (Cu 0 /C) was successfully synthesized from Cu-based metal–organic framework (Cu 3 (BTC) 2 ) through a pyrolysis method and applied to efficiently degrade sulfamethazine (SMT) at neutral pH under aeration condition. The performance of Cu 0 /C composite for the activation of molecular oxygen was evaluated based on the effect of different reaction parameters, such as, initial SMT concentration, initial pH, activator dosage and reaction temperature. The results showed a high efficiency for SMT removal over a broad pH range (3.0–7.0). Moreover, the Cu 0 /C composite exhibited excellent stability and reusability for SMT degradation, and a 96.7% SMT removal and a 68.8% total organic carbon (TOC) conversion were achieved at pH 5.8 after continuous three cycles. Combined with the determination results of reactive oxidizing species and physical-chemical characterization, cupryl species (Cu 3+ ) rather than OH produced by the reaction of the in-situ generated H 2 O 2 with Cu + were the major reactive species. Additionally, the possible reaction mechanism of Cu 0 /C activated oxygen was tentatively proposed.
研究领域:
环境科学
·
材料化学
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 1
·e202501680
·
IF 6.6
Jinlong Wu,Haiqiang Mu,Min Zhu,Xueru Zhao,Ting Zhang,Jiaxin Bai,Jin Zhang,Feng Li,Jing Li
Copper-based catalysts offer promise for CO 2 -to-C 2+ conversion but suffer from instability of Cu + species, which are active sites critical for enabling C−C coupling. In this work, we synthesized Lanthanum (La)-doped Cu x O (La-Cu x O) catalysts with varying La/Cu ratios to investigate how the interplay between doping-induced electronic effects and grain boundary (GB)-driven stabilization affects deep CO 2 reduction to C 2+ . Combined density functional theory calculations and in situ spectroscopic characterization reveal that the unique 4f orbital configuration and strong Lewis acidity facilitate charge transfer of La, stabilizing Cu + during CO 2 reduction reaction (CO 2 RR), while simultaneously inducing lattice distortion to increase GB density. This modulation preserves Cu + /Cu 0 interfaces while enhancing *CO dimerization kinetics. Furthermore, La doping boosts *CO coverage at GB-rich regions and lowers the C−C coupling barrier. The optimized La-Cu x O-2 catalyst (La/Cu = 0.224) achieves a 45.2% C 2 H 4 Faradaic efficiency (FE) and 75.4% C 2+ FE at −0.8 V RHE , with partial current densities of 87.5 and 146.7 mA cm −2 , respectively, surpassing undoped Cu x O. Remarkably, it retains more than 90% initial activity after 24 h operation, demonstrating exceptional stability. This work provides a rational strategy for stabilizing Cu + and tailoring pathways via rare-earth doping. Graphical La doping stabilizes Cu + /Cu 0 interfaces via electronic modulation and lattice distortion, enhancing grain boundary density in Cu x O catalysts for efficient CO 2 electroreduction. The optimized La-Cu x O-2 achieves 75.4% C 2+ Faradaic efficiency and 146.7 mA cm −2 partial current density at −0.8 V versus reversible hydrogen electrode, suppressing hydrogen evolution and enabling scalable CO 2 -to-C 2+ conversion.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xingyue Yang,Lei Wang,Shijie Zhou,Shilong Zhang,Yongfang Xu,Yujie Bian,Zhaowei Tian,Yusen Yang,Min Wei
Liquid organic hydrogen carriers (LOHC), which involve reversible catalytic hydrogenation/dehydrogenation cycles, have attracted considerable attention. This study investigates Cu/CuAlO x catalysts with unique Cu 0 –Cu + interfacial sites, which are prepared via structural topological transformation of layered double hydroxide (LDH) precursors. The optimized Cu/CuAlO x catalysts exhibit exceptional catalytic activity in 1,2,3,4-tetrahydroquinoline (THQ) dehydrogenation, achieving a complete conversion of THQ within 1.5 h and a turnover frequency (TOF) value amounts to 19.94 h −1 at 150 °C, which stands at the highest echelon compared with previously reported heterogeneous catalysts. Furthermore, the catalyst also exhibits excellent performance in quinoline hydrogenation (yield >99 %) after 6 h at 60 °C, and the TOF value reaches up to 7.01 h −1 . A comprehensive investigation based on XPS, TEM and XAFS verifies the dual active states Cu 0 and Cu + sites coexisting on nanoparticle surfaces. Both experimental studies ( in situ DRIFTS and XPS) and DFT calculations reveal the pivotal role of the Cu 0 − Cu + synergistic effect in dictating catalytic behavior: the Cu + species preferentially adsorb and activate the N − H bonds and C − H bonds in N-heterocycles; Whereas the Cu 0 site facilitates efficient reassociation of surface adsorbed H atoms and product desorption (H 2 ). This work exhibits substantial potential for implementation in hydrogen storage technologies, offering a viable pathway towards efficient LOHC utilization in clean energy systems.
研究领域:
催化化学
·
材料科学
·
氢气储存
·
化学反应工程
·
表面化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·
IF 3.9
Yongqiang Yao,Yongsheng Li,Zhengang Ke
P-xylene (PX) is an essential high-value chemical with a wide range of applications. The use of waste plastics to produce high-valuable chemicals is considered to be one of the most effective and sustainable waste plastic recycling routes. Herein, a simple and efficient CuAlOX catalyst was developed for the upcycling of waste PET plastic to PX. The yield of PX was up to 98%, and the catalyst can be reused for five runs without obvious deactivation. Mechanism investigation indicated that Cu+ and Cu0 are the possible active sites, and the best ratio of Cu+ to Cu0 is 2.9. The optimal Cu+ and Cu0 sites are favorable for the absorption of ester, carboxylic acid, and alcohol groups and the desorption of PX, which is key for the selective hydrodeoxygenation of PET to PX.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2022
·
IF 14.224
Huizhong Chi,Wenbiao Jin,Jianqiao Zhang,Yibin Xiu,Tao Xu
In recent years, there has been growing interest in the mechanism (radical or nonradical) of persulfate activation processes. In this study, the enhancement of naproxen (NPX) degradation in a Cu 0 /peroxymonosulfate (PMS) system by complexing reagents was investigated. Surprisingly, neocuproine (NCP) alters the nature of reactive species in the Cu 0 /PMS system. A high-valent copper species, Cu(III)-NCP, was found to dominate NPX degradation rather than radicals under acid conditions for the first time. Moreover, systematically designed experiments revealed that the Cu(III)-NCP complex was a strong selective oxidant that reacted with organics through a single electron transfer pathway. Meanwhile, the degradation efficiency of NPX was highly dependent on the solution pH and dosage of Cu 0 and NCP, but was irrelevant to the concentration of NPX. Additionally, the enhancement of NCP on other copper based PMS activation systems (i.e., Cu 2+ /HA/PMS and Cu 0 /HA/PMS systems) was investigated. Considering that the released copper can be removed by a simple precipitation method to meet the effluent standards, the new complex-enhanced Cu 0 /PMS system provided a new method to enhance the degradation efficiencies of pollutants by a copper-catalyzed Fenton-like system.
研究领域:
环境科学
·
化学工程
✓ 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）