INORGANIC CHEMISTRY
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2023
·
IF 4.6
Yu-Dong Shan,Song-Hai Wu,Yu-Le Wang,Cong Wang,Shao-Qi Zhi,Yong Liu,Xu Han
Selective oxidation of cyclohexane to cyclohexanol/cyclohexanone (KA–oil) is an important chemical process, which is still constrained by low conversion and selectivity and high energy consumption. In this study, Cu-doped mesoporous TiO2 (Cu-MT) has been successfully synthesized via calcinating MIL-125(Ti) doped with copper acetylacetonate, which shows high reactivity in selective oxidation of cyclohexane to KA–oil by persulfate (PS) with the desirable cyclohexane conversion of 16.8% and a selectivity of 98.0% under mild conditions and the low ratio of PS/cyclohexane of 1:1. A series of characterizations and density functional theory calculations reveal that the doped Cu(I,II) on Cu-MT is the reactive site for non-radical activation of PS with the moderate elongation of the O–O bond in PS, which then abstracts 1H (1H+ + 1e–) from cyclohexane to form Cy• and eventually KA–oil. This study gives new insight on the importance of moderately activated PS in selective oxidation of C–H.
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BIOCHEMICAL ENGINEERING JOURNAL
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2023
·
IF 3.9
Zibin Pan,Mengying Liu,Zuliang Chen
Acid mine drainage (AMD) has long been an environmental problem due to its acidic solution containing toxic metal ions. Despite the fact that a variety of nanomaterials have been devised to remove metallic contaminants from aqueous solutions, there are large differences between real AMD and aqueous solutions. Here, biosynthesized Fe/Cu nanoparticles (Fe/Cu NPs) functioned to remove metalloids and heavy metals from real AMD. The removal capacities of As, Mn, Ni, Cr and Cd were severally 1.305, 0.095, 0.027, 0.082 and 0.028 mg/g, which were consistent with the pseudo-first order kinetic model but not with the intraparticle diffusion model. After removal in AMD, the particle size and pore diameter of Fe/Cu NPs rose from 86.63 ± 0.88 nm and 56.36 nm to 110.53 ± 1.40 nm and 71.51 nm, respectively. Furthermore, organic substances on Fe/Cu NPs were able to adsorb heavy metals, namely Ni, Mn, and Cd from the AMD because they acted as an encapsulant able to maintain the stability of Fe/Cu NPs. Consequently, a mechanism for the removal of As and other heavy metal ions from AMD was proposed, one which was based on the rapid adsorption of multiple heavy metals through electrostatic interaction and ion exchange. This study provides a new and important insight into removing metalloids and heavy metals from AMD using green nanomaterials.
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Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Meng Hao,Yang Yusen,Shen Tianyao,Yin Zhiming,Wang Lei,Liu Wei,Yin Pan,Ren Zhen,Zheng Lirong,Zhang Jian,Xiao Feng-Shou,Wei Min
Copper-based catalysts serve as the predominant methanol steam reforming material although several fundamental issues remain ambiguous such as the identity of active center and the aspects of reaction mechanism. Herein, we prepare Cu/Cu(Al)O x catalysts with amorphous alumina-stabilized Cu 2 O adjoining Cu nanoparticle to provide Cu 0 −Cu + sites. The optimized catalyst exhibits 99.5% CH 3 OH conversion with a corresponding H 2 production rate of 110.8 μmol s −1 g cat −1 with stability over 300 h at 240 °C. A binary function correlation between the CH 3 OH reaction rate and surface concentrations of Cu 0 and Cu + is established based on kinetic studies. Intrinsic active sites in the catalyst are investigated with in situ spectroscopy characterization and theoretical calculations. Namely, we find that important oxygen-containing intermediates (CH 3 O* and HCOO*) adsorb at Cu 0 −Cu + sites with a moderate adsorption strength, which promotes electron transfer from the catalyst to surface species and significantly reduces the reaction barrier of the C−H bond cleavage in CH 3 O* and HCOO* intermediates.
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MATERIALS SCIENCE AND ENGINEERING A-STRUCTURAL MATERIALS PROPERTIES MICROSTRUCTURE AND PROCESSING
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2023
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IF 6.4
He Zhang,Guo-Hua Zhang
In this paper, using the ultrafine W-27.5 wt%Cu-2wt.%Mo-1.75 wt%Ni-0.75 wt%Fe-(0–1)wt.%CeO 2 alloy powders as raw materials, W–Cu–Mo–Ni–Fe–CeO 2 alloys with excellent performances were prepared by low temperature sintering . Two-step reduction method consisting of carbothermic pre-reduction and hydrogen deep deoxidation was used to produce ultrafine W–Cu–Mo–Ni–Fe–CeO 2 alloy powders with uniform distributed composition. All sintered blocks obtained relatively high densification degree (97.1 %∼99.2 %) to ensure the excellent comprehensive properties. Moreover, the existences of γ-(Cu, Ni, Fe) and W–Mo solid solutions ensured the alloy possessed a high mechanical strength . More importantly, the introduction of CeO 2 inhibited the growth of W–Mo grains. With increasing CeO 2 content from 0 wt% to 1 wt%, the W–Mo grain size decreased from 1.76 μm to 1.44 μm. Especially, alloy sample with the highest tensile and compressive strengths was obtained by adding 0.5 wt% CeO 2 , which were 602 MPa and 3187 MPa, respectively. Furthermore, owing to finer W–Mo grain size, this sample also possessed the maximum micro-hardness and bending strength of 482 H V and 1685 MPa, respectively. Nevertheless, the existences of Ni, Fe and CeO 2 also destroyed the electrical conductivities of the samples to some extent. Specifically, with increasing CeO 2 content from 0 wt% to 1 wt%, the electrical conductivity of the sample decreases from 32.56 %IACS to 30.16 %IACS.
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Journal of Environmental Chemical Engineering
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2023
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IF 7.7
Hang Yin,Qiuqiu Xiong,Miao Zhang,Bowen Wang,Fenge Zhang
In this study, magnetic composite microspheres (SCFP) were prepared by cross-linking chitosan (CS), sodium alginate (SA), poly(vinyl alcohol) (PVA), and ferric tetraoxide (Fe 3 O 4 ) in a CaCl 2 solution. CS and Fe 3 O 4 were encapsulated in gel spheres formed by cross-linking SA with Ca(II), while PVA facilitated the dispersion of CS in SA. SCFP was utilized as an adsorbent to remove Cu(II) from water. The effects of the initial pH of the solution, SCFP dosage, and initial Cu(II) concentration on the adsorption efficiency were investigated through batch experiments. The results demonstrated that the adsorption capacity reached 58.260 mg/g (removal rate = 97.1%) after 100 min of adsorption at a pH of 5. The removal rate remained above 90% even after 6 cycles of the cycling experiment. The incorporation of CS with other functional materials allowed SCFP to compensate for its inherent drawbacks such as low mechanical strength, poor acid resistance, and short service life. The pseudo-first-order kinetic model and Freundlich adsorption isotherm provided better descriptions of the adsorption process. A comprehensive analysis was conducted on the structure and adsorption mechanism of SCFP using characterization techniques such as SEM-EDS, FTIR , BET, XRD , etc. In summary, SCFP has the potential to be an excellent environmentally friendly material for the removal of Cu(II).
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PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
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2023
·Vol. 120
·期 44
·e2307320120
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IF 11.1
Yangyang Yu,Ye He,Ping Yan,Shengyao Wang,Fan Dong
The selective photocatalytic conversion of CO2 and H2O to high value-added C2H4 remains a great challenge, mainly attributed to the difficulties in C–C coupling of reaction intermediates and desorption of C2H4* intermediates from the catalyst surface. These two key issues can be simultaneously overcome by alloying Ag with Cu which gives enhanced activity to both reactions. Herein, we developed a facile stepwise photodeposition strategy to load Cu–Ag alloy sub-nanoclusters (ASNCs) on TiO2 for CO2 photoreduction to produce C2H4. The optimized catalyst exhibits a record-high C2H4 formation rate (1110.6 ± 82.5 μmol g−1 h−1) with selectivity of 49.1 ± 1.9%, which is an order-of-magnitude enhancement relative to current work for C2H4 photosynthesis. The in situ FT-IR spectra combined with DFT calculations reveal the synergistic effect of Cu and Ag in Cu–Ag ASNCs, which enable an excellent C–C coupling capability like Ag and promoted C2H4* desorption property like Cu, thus advancing the selective and efficient production of C2H4. The present work provides a deeper understanding on cluster chemistry and C–C coupling mechanism for CO2 reduction on ASNCs and develops a feasible strategy for photoreduction CO2 to C2 fuels or industrial feedstocks.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2023
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IF 5.2
Keliang Song,Zhipeng Liu,Aoshuang Yang,Yongsheng Li,Fangfang He,Zhuoni Jiang,Xiaoan Li,Zhengguo Chen,Wenbin Yang
Hydrated salt phase change materials (PCMs) have the advantages of high energy storage density and low cost, and have great application prospects in the field of phase change energy storage. However, the problems of supercooling, phase separation and leakage of hydrated salt PCMs limit their further applications. In this work, we designed and fabricated Cu-coated melamine foam (MF)/barium hydroxide octahydrate (BHO) shape-stabilized phase change materials (SSPCMs) with low supercooling. MF was used as supporting material and Cu as a nucleating agent and thermal conductivity enhancer by loading it onto MF via electroless plating . BHO was then encapsulated into the MF@Cu skeleton through vacuum impregnation to obtain BHO@MF@Cu SSPCMs. The results demonstrated that BHO@MF@Cu SSPCMs not only present very low supercooling degree of 0.12 °C and high thermal energy capacity of 247 J/g, but maintained a latent heat of phase transition of 229.3 J/g with little change in enthalpy after 100 thermal cycles. Moreover, compared to BHO, SSPCMs exhibited high thermal conductivity of 1.687 W m −1 K −1 , excellent shape stability, and thermal cycling stability. In summary, BHO@MF@Cu SSPCMs with low supercooling degree were prepared by electroless plating and vacuum impregnation in this study, which provides a new strategy to reduce the supercooling degree of hydrated salt PCMs.
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JOURNAL OF HAZARDOUS MATERIALS
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2023
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IF 13.6
Mingyi Liu,Hanchun Chen,Pengfei Xiao,Haodong Ji
Copper-manganese composite metal oxides (CuMnO y ) were prepared by hydrolysis-driven oxidation-reduction method and used to activate sulfite to degrade chlortetracycline hydrochloride (CTC) for the first time. The Jahn-Teller ions Mn 3+ and Cu 2+ exist in CuMnO y , which form a solid electric charge transport redox system and ensure the continuous generation of reactive oxygen species (ROS). Through the systematic study of the experimental parameters such as sulfite concentration, catalyst metal molar ratio, catalyst amounts and initial pH, the optimal degradation rate of CTC could reach 91.74% within 10 min and 94.46% after 30 min. The major reactive radicals were determined by radical quenching experiments and electron paramagnetic resonance (EPR) trapping techniques, and it was confirmed that SO 4 •- and •O 2 - played a nonnegligible role in the process of degrading CTC. Density functional theory (DFT) calculations show that higher Fukui indices ( f - and f 0 ) of CTC sites are more vulnerable to free radical attack. CuMnO y has low CTC degradation intermediate toxicity, high catalytic performance, good anti-interference ability, reusability and stability, and possesses decent application potential in the actual water treatment field.
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NEW JOURNAL OF CHEMISTRY
·
2023
·Vol. 47
·期 44
·20336-20343
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IF 3.3
Meihui Lu,Aichen Dong,Xinyang Li,Xuanqi Liu,Ziqing Zhang,Tao Tian,Liqiang Jing
Semiconductor photocatalysis is a potential solution to meet energy needs with green and inexhaustible solar energy. However, designing efficient and stable photocatalysts is a challenging task due to the limited ability to effectively separate electrons and holes. In this paper, by using a straightforward ethanol dispersion technique, we were able to combine ultrathin layered Cu-TCPP MOFs with g-C3N4 nanosheets, resulting in the creation of an extremely effective nano-composite photocatalyst with exceptional UV-vis activity. CT/CN heterojunctions displayed remarkable photocatalytic efficacy for the production of H2, with 3CT/CN showcasing a five-fold enhancement in photoactivity as compared to the unadorned g-C3N4. Based on the results of photoluminescence spectroscopy, electrochemical impedance spectroscopy, and electrochemical reduction, the considerably improved charge transfer and separation, together with the possible catalytic capability of uniformly distributed metal nodes in Cu-TCPP, are believed to be the underlying reason for the observed exceptional photoactivity. After thorough analysis, a potential process for charge transfer and segregation between g-C3N4 and Cu-TCPP has been suggested.
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Nano-Micro Letters
·
2023
·Vol. 15
·期 1
·1-15
·
IF 26.6
Li Minhan,Zhang Fangzhou,Kuang Min,Ma Yuanyuan,Liao Ting,Sun Ziqi,Luo Wei,Jiang Wan,Yang Jianping
Electrochemical reduction of CO 2 into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO 2 capture and utilization, resulting from their high catalytic activity and selectivity. The mobility and accessibility of active sites in Cu-based catalysts significantly hinder the development of efficient Cu-based catalysts for CO 2 electrochemical reduction reaction (CO 2 RR). Herein, a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride (g-C 3 N 4 ) as the active sites for CO 2 -to-CH 4 conversion in CO 2 RR. By regulating the coordination and density of Cu sites in g-C 3 N 4 , an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH 4 Faraday efficiency of 49.04% and produces the products with a high CH 4 /C 2 H 4 ratio over 9. This work provides the first experimental study on g-C 3 N 4 -supported single Cu atom catalyst for efficient CH 4 production from CO 2 RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO 2 RR by engineering Cu active sites in 2D materials with porous crystal structures.
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PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
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2023
·
IF 7.8
Zibin Pan,Qingqiang Gao,Zuliang Chen
The elimination of arsenic (As) from arsenic-contaminated mine groundwater has become a worldwide problem because it causes environmental degradation and poses serious risks to human health. In this study, biosynthesized Fe/Cu nanoparticles (Fe/Cu NPs) were used for the simultaneous elimination of As(Ⅲ) and As(Ⅴ) from aqueous solution, resulting in their maximum amounts removed at 8.5 and 17.5 mg/g, respectively. SEM, FTIR, and XPS characterizations indicate that the Fe component on the Fe/Cu NPs acted as an adsorption and catalyst, while the Cu component mainly developed into a co-precipitation reaction with the As species, also facilitating the Fe catalytic processed. Meanwhile, adsorption isotherms , kinetics, and DFT calculations reveal that the removal of As(Ⅲ) was primarily physical/chemical adsorption and oxidation , while the elimination of As(Ⅴ) was co-precipitation and chemisorption. The most stable adsorption site, receiving 0.252 and 0.306 electrons from As(Ⅲ) and As(Ⅴ), respectively, was the unsaturated complexes of iron on the Fe/Cu NPs. Finally, the measurements and XPS results of Fe/Cu NPs in the treatment of groundwater show that the reduced capacity to remove As was attributed to a complex reaction system that disrupted the function of the Cu component, including co-precipitation and made the catalytic process possible. This explains there are differences in the reaction processes of biosynthetic Cu/Fe NPs in aqueous solution and groundwater.
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Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Mao Qiqi,Mu Xu,Wang Wenxin,Deng Kai,Yu Hongjie,Wang Ziqiang,Xu You,Wang Liang,Wang Hongjing
Organic electrocatalytic conversion is an essential pathway for the green conversion of low-cost organic compounds to high-value chemicals, which urgently demands the development of efficient electrocatalysts. Here, we report a Cu single-atom dispersed Rh metallene arrays on Cu foam for cathodic nitrobenzene electroreduction reaction and anodic methanol oxidation reaction. In the coupled electrocatalytic system, the Cu single-atom -Rh metallene arrays on Cu foam requires only the low voltages of 1.18 V to reach current densities of 100 mA cm −2 for generating aniline and formate, with up to ~100% of nitrobenzene conversion/ aniline selectivity and over ~90% of formate Faraday efficiency, achieving synthesis of high-value chemicals. Density functional theory calculations reveal the electron effect between Cu single-atom and Rh host and catalytic reaction mechanism. The synergistic catalytic effect and H*-spillover effect can improve catalytic reaction process and reduce energy barrier for reaction process, thus enhancing electrocatalytic reaction activity and target product selectivity.
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