Catalysis Science & Technology
·
2019
·Vol. 9
·期 10
·2673-2681
·
IF 5.726
Bing Hu,Yazhi Yin,Zixin Zhong,Dengdeng Wu,Guoliang Liu,Xinlin Hong
Maximizing the Cu–ZnO interface is regarded as the best strategy to promote methanol synthesis activity over CuZn catalysts. Reducing the ZnO particle size can enhance the Cu–ZnO interaction, but its synthesis with a sub-5 nm size still remains a challenge. Moreover, the fabrication of an active powder catalyst with an inverse ZnO/Cu configuration is still very rare. In this work, we report a facile synthesis of inverse ZnO/Cu catalysts by direct calcination of Cu@ZIF-8 (zeolitic imidazolate framework-8). The particle size of ZnO and Cu can be tuned by changing the Cu loading as well as the calcination temperature. Importantly, inverse ZnO/Cu catalysts with sub-5 nm ZnO were obtained under gentle calcination at 623 K. In the CO2 hydrogenation reaction, the highest methanol synthesis activity reached 933 g kgcat−1 h−1 at 533 K and 4.5 MPa, with a high turnover frequency (TOF) of 0.013 s−1, over an optimized C2Z-623 catalyst, which exceeds the commercial CuZnAl catalyst (HiFuel R120, Johnson Matthey) and has ranked the top reported value over advanced CuZn catalysts under comparable conditions. Such excellent activity is attributed to the inverse structure of Cu particles covered by sub-5 nm ZnO, which promotes the intimate Cu–ZnO interface with enhanced SMSI. Moreover, we find that the methanol turnover frequency (TOF) monotonically increases with decreasing the particle size of ZnO as well as Cu. It is proposed that reducing the ZnO size favors the spillover of reducible ZnOx species onto the Cu surface while lowering the Cu size is responsible for the enhanced amount of exposed Cu steps for accommodating Zn species, both of which could facilitate the formation of Zn covered Cu steps as active sites for methanol synthesis.
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
Chem
·
2023
·
IF 23.5
Rongming Cai,Mingzi Sun,Fei Yang,Min Ju,Yanpeng Chen,M. Danny Gu,Bolong Huang,Shihe Yang
Summary By leveraging a Cu(OH)F precursor, we construct a disk-like Cu(I)/Cu(0) interface model (P-Cu x /Cu 2 OF) composed of F-stabilized Cu(I) shell and Cu(0) core by one-step pulsed potential conversion. The interfacial region is shown to facilitate ethanol formation, guaranteeing a high FE(C 2+ ) of up to 80.2%. Tuning the Cu(I)/Cu(0) ratio enhances the ethanol yield by 18.5-fold over pure P-Cu, with the corresponding partial current density (j ethanol ) reaching up to 128 mA/cm 2 . This is enabled by a 3.6-fold boost in selectivity for the ethanol product (35.4%) and an overall 7.8-fold boost in activity ( j C 2 + up to 288 mA/cm 2 ). The interactions between P-Cu and Cu 2 OF upshift the d-band center of Cu sites on the interface region, which is critical to asymmetrical C-C coupling to form OCCOH∗, concurrent with a lowered energy barrier for ethanol formation. On the other hand, the ethylene-forming symmetrical C-C coupling occurs primarily on P-Cu away from the Cu(I)/Cu(0) interface.
研究领域:
材料科学
·
电化学
·
催化
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Hongyu Niu,Yuan Cheng,Chuang Li,Shaojie Li,Jingjie Luo,Changhai Liang
Rational design of promising Cu catalyst requires better understanding of the Cu–support perimeter for reactions such as hydrogenation rearrangement of furfural─a pivotal and alternative transformation to produce cyclopentanol. Herein, a series of Cu catalysts with constructed Cu-M-Ox interfaces (M = Zn or Al) have been synthesized. In freshly reduced Cu/ZnO-Alx samples, aluminum species was enriched surrounding Cu. The Cu-Al-Ox contacting interface was formed, and the CuAl2O4 spinal structure was detected as a combining consequence only if Zn and Al species coexisted. The specific metal–support synergistic interaction and Cu-Al-Ox contacting interface simultaneously aroused the enhanced redox property and large number of surface acid sites, facilitating the adsorption/activation of hydrogen and reactants. During the reaction, Al2O3 retreating from the Cu-Al-Ox interface caused the replacement of Cu-Al-Ox by new Cu-Zn-Ox interface, which was directly correlated with the irreversibly changed chemical structure and decreased cyclopentanol yield, although the furfural conversion was well sustained. In this work, we confirmed that supported copper catalysts were competent for the activation and conversion of furfural, with the turnover frequency reaching 28.1 h–1 by the Cu/ZnO-Al3 sample at temperatures as low as 90 °C. The further transformation of cyclopentanone to cyclopentanol was largely depending on the maintenance of a steady Cu-Al-Ox contacting interface.
研究领域:
催化
·
化学工程
·
材料科学
·
有机化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Xiaoyu Hu,Fengyun Ding,Renjin Xiong,Yongtao An,Xingwen Feng,Jiangfeng Song,Linsen Zhou,Peilong Li,Changlun Chen
Realizing ideal deuterium separation from isotopic mixtures remains a daunting challenge because of their almost identical sizes, shapes, and physicochemical properties. Using the quantum sieving effect in porous materials with suitable pore size and open metal sites (OMSs) enables efficient hydrogen isotope separation. Herein, synthetic HKUST-1-derived microporous mixed-valence Cu(I)Cu(II)-BTC (BTC = benzene-1,3,5-tricarboxylate), featuring a unique network of distinct Cu(I) and Cu(II) coordination sites, can remarkably boost the D2/H2 isotope separation, which has a high selectivity (SD2/H2) of 37.9 at 30 K, in comparison with HKUST-1 and other porous materials. Density functional theory (DFT) calculations indicate that the introduction of Cu(I) macrocycles in the framework decreases the pore size and further leads to relatively enhanced interaction of H2/D2 molecules on Cu(II) sites. The significantly enhanced selectivity of Cu(I)Cu(II)-BTC at 30 K can be mainly attributed to the synergistic effect of kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS). The results reveal that Cu(I) OMSs exhibit counterintuitive behaviors and play a crucial role in tuning quantum sieving without a complex structural design, which provides a deeper insight into quantum sieving mechanisms and a new strategy for the intelligent design of highly efficient isotope systems.
研究领域:
材料科学
·
物理化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICAL CHEMISTRY
·
2019
·
IF 6.35
Li Fu,Bin Zhang,Xiaoyan Long,Kena Fu,Xuwen Gao,Guizheng Zou
Screening a novel electrochemiluminescence (ECL) system is crucial to ECL evolution. Herein, an efficient ECL system with less interference and environmental concern under physiological condition is developed via a unique internal Cu(I)/Cu(II) couple cycling amplified strategy by employing the glutathione- and citrate-capped copper indium sulfide (CIS)/ZnS nanocrystals (NCs) as electrochemiluminophore and N2H4·H2O as co-reactant. CIS/ZnS NCs can be electrochemically injected with valence band (VB) hole at 0.46 and 0.87 V (vs Ag/AgCl), and then achieve the same hole-injected states by relocalizing VB holes with the Cu(I) species inside of CIS/ZnS NCs to form internal Cu(II) defects, while each N2H4·H2O molecule can be successively oxidized to two more reducing species N2H3• and N2H2 around 0.10 V, and inject conduction band (CB) electron onto CIS/ZnS NCs for triple times. The internal Cu(I)/Cu(II) couple cycling involved radiative-charge recombination between these VB hole and CB electron eventually enables two efficient near-infrared ECL processes (around 731 nm) at 0.55 and 0.87 V, in which each single nanocrystal may participate in multiple ECL reaction cycles to produce multiple photons for amplified ECL, similar to the tris(bipyridyl)ruthenium(III) based ECL system. The low-triggering-potential ECL process at 0.55 V can be utilized to selectively determine Cu(II) with a wide linear range from 10 and 1500 nM and a limit of detection of 5 nM (S/N = 3). This work presents a NCs engineering and co-reactant selecting combined strategy for further ECL evolution.
研究领域:
分析化学
·
纳米技术
·
电化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Mingxian Duan,Yeshuang Wang,Huiling Fan,Zhelin Su,Chao Yang,Jiawei Kou,Ju Shangguan
Thiophene (C 4 H 4 S) removal from coke oven gas is critical to its subsequent high valuable utilization but remains a challenge. MOF-199 was considered as a promising candidate for C 4 H 4 S adsorption removal owing to its nature of enriched opened Cu sites. However, the presence of mixed valence of Cu(II) and Cu(I) in MOF-199 makes it puzzling to their respective contribution to the removal of C 4 H 4 S. Herein, a series of MOF-199 with different Cu(I) contents were synthesized using different methods, including hydrothermal, solution diffusion, and ultrasonic, and their C 4 H 4 S adsorption performance were investigated. The respective contributions of Cu(II) and Cu(I) to the C 4 H 4 S removal was systematically discussed. The collected results indicated that although the samples prepared with different methods present a remarkable difference in textural characters, the latter was found to have a negligible influence on the C 4 H 4 S removal owing to MOF-199(H) affording an inferior surface area and pore volumes but performing the best C 4 H 4 S removal capacity of 53.7 mg S/g. The co-adsorption results of CH 3 SCH 3 and C 4 H 4 S indicated that the excellent performance of MOF-199(H) mainly attributed to the presence of Cu(I), which provides active sites for C 4 H 4 S adsorption through π complex coordination. Cu(II) species was also found to the C 4 H 4 S adsorption via soft-acid-base coordinated interaction, but its contribution is 8.3 mg S/g, only accounting for 15.5 %. Additionally, the adsorption of C 4 H 4 S on MOF-199(H) was found to follow the intra-particle diffusion model and the Langmuir models. Moreover, MOF-199(H) also exhibited an excellent regeneration performance due to the weak interaction between C 4 H 4 S and their opened Cu sites, the C 4 H 4 S adsorption capacity still reaches 50.6 mg S/g after three regeneration cycles, about 94 % of its initial value. The results collected in this study will provide new insights for the manipulation of performance of C 4 H 4 S adsorption on the MOF-199.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 98
·95740-95746
·
IF 3.289
Lili Bie,Xue Luo,Qingqing He,Daiping He,Yan Liu,Ping Jiang
Hierarchical Cu/Cu(OH)2 nanorod arrays grown on commercially available Cu foam (Cu/Cu(OH)2 NRA/CF) was prepared via a three-step strategy involving the wet chemical synthesis of Cu(OH)2 NRA/CF, a chemical reduction reaction for conversion from Cu(OH)2 NRA/CF to Cu NRA/CF, and finally galvanostatic anodization to grow Cu(OH)2 nanoparticles on Cu NRA/CF. Hierarchical Cu/Cu(OH)2 NRA/CF shows high catalytic activity towards glucose oxidation in an alkaline solution and can serve as a promising electrode material for enzyme-free glucose sensing. At an applied potential of +0.5 V, the sensor showed a broad detection range of 0.001–1.0 mM, a high sensitivity of 9.18 mA mM−1 cm−2, and a low detection limit of 0.45 μM (S/N = 3). Furthermore, the sensor exhibits excellent selectivity against common interferents and good reliability for glucose detection in human serum samples.
研究领域:
材料科学
·
生物医学工程
·
电化学传感
✓ 已验证
产品关联
DOI
高影响因子
Materials
·
2022
·Vol. 15
·期 5
·1846
·
IF 3.748
Haiyao Cao,Zaiji Zhan,Xiangzhe Lv
Ti3AlC2presents a hexagonal layered crystal structure and bridges the gap between metallic and ceramic properties, and Gadolinia (Gd2O3) has excellent thermodynamic stability, which make them potentially attractive as dispersive phases for Cu matrix composites. In this paper, Cu@Ti3AlC2-Gd2O3/Cu composites, Ti3AlC2-Gd2O3/Cu composites, and Gd2O3/Cu composites were prepared by electroless Cu plating, internal oxidation, and vacuum hot press sintering. The microstructure and the effect of the Cu plating on the properties of the Cu@Ti3AlC2-Gd2O3/Cu composites were discussed. The results showed that a Cu plating with a thickness of about 0.67 μm was successfully plated onto the surface of Ti3AlC2particles. The ex situ Ti3AlC2particles were distributed at the Cu grain boundary, while the in situ Gd2O3particles with a grain size of 20 nm were dispersed in the Cu grains. The electroless Cu plating onto the surface of the Ti3AlC2particles effectively reduces their surfactivity and improves the surface contacting state between the Cu@Ti3AlC2particles and the Cu matrix, and reduces electron scattering, so that the tensile strength reached 378.9 MPa, meanwhile, the electrical conductivity and elongation of the Cu matrix composites was maintained at 93.6 IACS% and 17.6%.Keywords:Cu@Ti3AlC2-Gd2O3/Cu composites;electroless Cu plating;microstructure;electrical conductivity;mechanical properties
研究领域:
材料科学
·
冶金工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Carbon Energy
·
2025
·
IF 24.2
Mengmeng Ma,Runkang Lin,Kaige Huang,Shizhong Yue,Maohong Fan,Zhijie Wang,Shengchun Qu
Functionalization has emerged as a pivotal endeavor to tailor the surface properties of photocatalysts. We propose a facile amine functionalization strategy to establish a Cu−In−Zn−S (CIZS)/NiS x hybrid with covalent bonds using individual ethylenediamine (EDA) molecules. Our approach witnesses a remarkable photocatalytic hydrogen evolution (PHE) competence of 65.93 mmol g −1 h −1 driven by visible light, the highest value yielded by CIZS to date. X-ray absorption spectra of CIZS and density functional theory (DFT) calculations confirm the crucial amine N→Cu coordination after amine functionalization. The new emerging coordination via lone-pair electron donation profitably accesses the regulation of the coordination environment, electronic structures, and carrier behavior. Moreover, individual EDA molecule with two-terminal −NH 2 group serves as a molecular bridge to hybrid CIZS and NiS x cocatalyst via N→Cu and N→Ni coordination, favorably promoting efficient charge transport. This study provides advances in practical functionalizing photocatalysts.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMOSPHERE
·
2021
·
IF 7.086
Qing Zhao,Xiao Zhang,Dezhi Huang,Long Chen,Shuxin Li,Jean-Marc Chovelon,Lei Zhou,Guangli Xiu
Cu(II) is generally considered to be a poor activator for PMS decomposition, thus the potential impact of trace Cu(II) on PMS induced oxidation of typical pollutants is always overlooked. In this study, we reported that trace Cu(II) could significantly promote PMS induced degradation of four selected sulfonamide antibiotics (SAs), namely, sulfamehoxazole (SMX), sulfathiazole (STZ), sulfamerazine (SMZ), and sulfamonomethoxine (SMM). Different from conventional PMS-induced oxidation process, high-valent Cu(III) was ascertained as the primary reactive intermediate for SAs degradation, which was confirmed by raman tests and electron paramagnetic resonance (EPR). High concentrations of Cu(II) or PMS were beneficial to degradation of the selected contaminants. In PMS/Cu(II) oxidation system, all the selected SAs could undergo several different degradation pathways including continuous oxidation of aniline group, hydroxylation and S–N bond cleavage. In particular, for six-membered SAs, such as SMZ and SMM, a SO 2 extrusion pathway was also detected. The potential mechanism for Cu(III) formation was also proposed, which was believed to be highly related to the nature of the SAs. Hydroxylamine-SAs (N 4 –OH–SAs), generated from direct PMS oxidation of SAs, was deduced as the “promoter” for the whole oxidation process. And the generation of Cu(III) was likely to proceed through the interaction between PMS and Cu(I), which possibly derived from the reduction of Cu(II) by N 4 –OH–SAs. The results obtained in this study validated the contribution of Cu(III) to the elimination of pollutants and expanded our understanding of the oxidation process of PMS in the presence of trace amounts of Cu(II).
研究领域:
环境化学
·
水处理
·
污染物降解
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Yichen Ding,Dongya Li,Shiyu Zuo,Zeyu Guan,Su Ding
The synergistic effect of radicals and non-radical pathways has attracted much attention for pollutant removal in complex water environments. A novel B-doped CuO/Cu 2 O composite material (B-Cu x O) was synthesized to activate PMS for the degradation of bisphenol A (BPA). XPS and FT-IR proved that B was doped into the Cu x O, which changed the proportion of Cu(Ⅱ) and Cu(Ⅰ). As a result, the cycle of Cu(Ⅱ)/Cu(Ⅰ) was promoted and the kinetic degradation rate of BPA increased by 12 times. The radicals quenching experiments and EPR verified the effects of radicals (·OH and SO 4 ·- ) and non-radical ( 1 O 2 ) pathways in the pollution degradation processes. The results show that B doping accelerated the Cu(Ⅱ)/Cu(Ⅰ) cycle, and at the same time realized the synergistic effect of radicals and non-radical. The PMS/B-Cu x O system exhibited consistent performance in a wide pH range of 5–11. The toxicity evaluation of the transformation products among BPA solutions was studied. This study provided a novel method for accelerating the catalysis of radicals and non-radical synergy.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
CHEMOSPHERE
·
2019
·
IF 5.108
Jiajun Long,Longqian Xu,Linghui Zhao,Huaqiang Chu,Yunfeng Mao,Deli Wu
In this study, Cu(0) was synthesized with NaBH 4 as a reducing agent for Cu(II) and used to activate dissolved molecular oxygen (O 2 ) under acidic conditions. The Cu(0) synthesized had much higher activity than the purchased. The roles of Cu was clarified and the formation of reactive oxygen species was discussed through direct detection for the first time. By detecting the valence change of Cu in a CuO system, Bisphenol A (BPA) was found to accelerate the transformation of Cu(II) to Cu(I). Besides, the evidence from electron spin resonance (ESR) studies and scavenging tests revealed the new roles of Cu(0) that Cu(0) could not only convert O 2 to produce ·O 2 − , but also catalyze H 2 O 2 to ·OH. The results from this study offer evidence of new reaction pathways in Cu-activated O 2 systems and deepen understanding of the reaction between Cu species and O 2 .
研究领域:
环境科学
·
化学
·
材料科学
✓ 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）