International Journal of Minerals Metallurgy and Materials
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2025
·Vol. 32
·期 12
·3072-3085
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IF 7.2
Zhang Qian,Liu Bo,An Changcong,Li Qiong,Liu Jiling,Wei Siyu,Fan Jiaxing,Sun Zhe,Zhang Dichuan,Pulatov Bakhtiyor
The effect of heavy metals on the properties and hydration of blast furnace slag–cement composites (BFS-CC) remain unclear. In this study, two BFS-CC (denoted as DBFS-CC and WBFS-CC) were prepared by dry and wet grinding of BFS, respectively. The effect of Cu(II) on BFS-CC’s properties and hydration was investigated by adding representative copper contaminants (CuO, CuCl 2 , and CuS) to the composites. Adding 1.0wt% CuO and 0.5wt% CuS increased the 3-d compressive strength of DBFS-CC by 14.9% and 5.7%, respectively, but suppressed the 3-d strength of WBFS-CC. This trend reversed at 28-d curing, where adding 1.5wt% CuO, 2.0wt% CuCl 2 , and 1.5wt% CuS enhanced the compressive strength of WBFS-CC by 23.4%, 6.2%, and 13.6%, respectively, but adversely affected the strength of DBFS-CC. For 28-d hydration, adding CuCl 2 decreased the hydration degree of DBFS-CC but enhanced that of WBFS-CC. Adding CuO promoted the hydration degree of both composites, while adding CuS exhibited inhibitory effects. DBFS-CC immobilized CuCl 2 better due to a higher hydration degree, while WBFS-CC immobilized CuO and CuS better due to having finer unhydrated BFS particles and a denser matrix. This study not only focuses on the Cu(II) immobilization effect but also reveals the differential effects of Cu(II) species on the hydration process, providing novel insights into heavy metal interactions in BFS-CC systems and their safe disposal.
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CHEMISTRY OF MATERIALS
·
2022
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IF 10.508
Xueyang Han,Zhang Liu,Meng Cao,Haonan Ren,Chun Du,Fan Yang,Bin Shan,Rong Chen
Cu-based materials are promising catalysts for the electrochemical CO2 reduction reaction (CO2RR). However, they frequently have a low Faradaic efficiency (FE) and selectivity for a specific single product. Particularly, the precise construction of a Cu microenvironment is a great challenge in the design and fabrication of excellent Cu-based CO2RR catalysts. In order to systematically regulate the Cu metal site environment, the classic HKUST-1 containing paddle-wheel Cu coordination nodes was used as a template and modified with the atomic layer infiltration (ALI) technique in this work. A detailed structural analysis shows that a uniform distribution of Zn–O–Zn sites is introduced into HKUST-1 and linked to neighboring Cu nodes without changing the original morphology and structure. In comparison with pristine HKUST-1, the FE for CO increases from 20–30% to 70–80% for the ALI-modified HKUST-1 within the tested overpotential range. Density functional theory (DFT) simulations prove that the modification with Zn–O–Zn by ALI enhances the adsorption enthalpy of CO2 and strengthens the bonding interaction between the COOH* intermediate and the adsorption center, thereby reducing the whole reaction barrier and accelerating CO formation. The proposed ALI technique elucidates the reliance of CO2RR selectivity on the Cu microenvironment and provides a platform for regulating the coordination environments of Cu or other metal-based electrocatalysts to facilitate the high selectivity of CO2RR in the future.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2020
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IF 5.774
Longqian Xu,Linghui Zhao,Yunfeng Mao,Zhen Zhou,Deli Wu
Copper-iron bimetallic material shows a high reactive activity in dioxygen activation processes (DOAs) but presents a significant challenge for enhancing superoxide radical ( • O 2 − ) generation. In this study, a practical strategy was developed to enhance • O 2 − generation for BPA degradation using a zeolite-supported Cu-Fe bimetallic system (called Cu/Fe@zeolite), which was simply prepared by impregnation method. The results verified that the Cu(I) regeneration at the zeolite surface contributes • O 2 − generation and the H 2 O 2 that is further generated induces • OH production via a further Fenton reaction. In the reaction process, the initial generation of • O 2 − was primarily enhanced by the Cu(I) loaded onto the zeolite surface and the adsorbed BPA was easily degraded by the •OH. Under optimal operating conditions (i.e., Cu/Fe@zeolite = 3 g/L, Cu:Fe = 1:2, pH = 5, t = 120 min), it was found that 87% of BPA can be removed from wastewater. It is also important to note that the weak alkali buffering property of zeolite not only provides BPA adsorption sites under acidic conditions but also accelerates the precipitation efficiency for metallic ions and reduced the adverse effect of metallic residue on the effluent quality.
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RSC Advances
·
2019
·Vol. 9
·期 71
·41561-41568
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IF 3.049
Cuifeng Jiang,Xiaoxiu Wei,Shuai Bao,Huajian Tu,Wei Wang
Nanomaterial-based artificial peroxidase has attracted extensive interests due to their distinct advantages over natural counterpart. Cu@Au/Pt and Cu@Ag/Pt nanocomposite with rambutan-like structure were prepared and discovered to function like peroxidase, which was illustrated by catalyzing the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) accompanied with a blue color change. Steady-state investigation indicates that the catalytic kinetics of Cu@Au/Pt and Cu@Ag/Pt all followed typical Michaelis–Menten behaviors and Cu@Au/Pt showed a strong affinity for H2O2, while Cu@Ag/Pt showed strong affinity for TMB. The color change and absorbance intensity strongly depend on the concentration of H2O2, thus the direct determination of H2O2 and indirect detection of glucose were demonstrated using Cu@Au/Pt with a detection limit of 1.5 μM and 6 μM, respectively. What is more important, the method was applied for detection of glucose in 50% fetal bovine serum with a detection limit of 80 μM, which is much lower than the lowest glucose content in blood for diabetes (7 mM). Moreover, the Cu@Au/Pt nanocomposite were also successfully applied for sensing L-cysteine because of the inhibition effect. Considering the good peroxidase-like activity and novel structure, Cu@Au(Ag)/Pt is expected to have a wide range of applications in bioassays and biocatalysis.
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CHEMOSPHERE
·
2019
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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 .
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CATALYSIS TODAY
·
2019
·
IF 4.888
Yuhan Ma,Huawang Zhao,Cuijuan Zhang,Yingnan Zhao,Hong Chen,Yongdan Li
Cu-SSZ-13 is a highly active catalyst to remove NO x in the emission of diesel-powered engine. However, the enhancement of its stability in high-temperature (HT) hydrothermal conditions is a well-known challenge in application. This work presents a simple strategy to significantly improve its hydrothermal stability under HT hydrothermal condition by mechanically mixing another CHA type zeolite, Cu-SAPO-34. Both the two zeolites are synthesized via one-pot method, mixed in different ratios, and treated in 10% H 2 O/air at 750 °C for 16 h. The mixed samples are characterized before and after the hydrothermal treatment, and tested in NH 3 -SCR from 150 to 550 °C. The results show the activity of the hydrothermally treated catalysts increases with the increase of the amount of Cu-SAPO-34 up to 50 wt% in the mixed sample. The hydrothermal stability of Cu-SSZ-13 is obviously enhanced by mixing with Cu-SAPO-34. The dealumination is suppressed during the hydrothermal treatment; the framework and the isolated Cu 2+ sites are largely maintained in Cu-SSZ-13. This is attributed to the interaction between the two CHA zeolites during the hydrothermal treatment. We propose the delivery of extra-framework P species from Cu-SAPO-34 to Cu-SSZ-13 is critical to enhance the HT hydrothermal stability.
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MICROPOROUS AND MESOPOROUS MATERIALS
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2017
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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.
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ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Zhijian Chen,Zhenghui Ma,Guoli Fan,Feng Li
Presently, realizing high ethanol selectivity in CO2 electroreduction remains challenging due to difficult C–C coupling and fierce product competition. In this work, we report an innovative approach for improving the efficiency of Cu-based electrocatalysts in ethanol generation from electrocatalytic CO2 reduction using a crystal plane modification strategy. These novel Cu-based electrocatalysts were fabricated by electrochemically activating three-dimensional (3D) flower-like CuO micro/nanostructures grown in situ on copper foils and modifying with surfactants. It was demonstrated that the fabricated Cu-based electrocatalyst featured a predominantly exposed Cu(100) surface loaded with high-density Cu nanoparticles (NPs). The optimal Cu-based electrocatalyst displayed considerably improved CO2 electroreduction performance, with a Faraday efficiency of 37.9% for ethanol and a maximum Faraday efficiency of 68.0% for C2+ products at −1.4 V vs RHE in an H-cell, accompanied by a high current density of 69.9 mA·cm–2, much better than the particulate Cu-based electrocatalyst. It was unveiled that the Cu(100)-rich surface of nanoscale petals with abundant under-coordinated copper atoms from CuNPs was conducive to the formation and stabilization of key *CH3CHO and *OC2H5 intermediates, thereby promoting ethanol generation. This study highlighted the critical role of CuNP-loaded Cu(100) surface structures on structured Cu-based electrocatalysts in enhancing ethanol production for the CO2 electroreduction process.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Jicheng Wang,Yanhong Quan,Linjie Li,Shunan Yin,Xinxin Ding,Jun Ren
A series of Cu/SBA-15 catalysts with different Cu loadings are prepared by the ammonia evaporation method for the liquid-phase hydrogenation of furfural (FF) to furfuryl alcohol (FA). The results show that the supported Cu loading influences the structure and catalytic activity during FF hydrogenation. The 20Cu/SBA-15 catalyst shows the optimum performance with 99.3 % FF conversion, 99.0 % selectivity to FA, nearly pure FA product, and a turnover frequency reaching up to 81.7h −1 . The effect of Cu loading can be related to Cu dispersion and the interaction between the metal and support, which further promotes the surface Cu + /Cu 0 ratio. Additionally, the correlation of FF conversion with Cu + /Cu 0 ratio confirms that the excellent performance of 20Cu/SBA-15 is mainly derived from the synergy of Cu + and Cu 0 species, although the range of performance is not large. Finally, the optimal reaction conditions are screened using a reaction temperature of 150 °C, a reaction pressure of 4 MPa, a catalyst dosage of 0.1 g, and a reaction time of 60 min. The present study confirms that the Cu loading has a significant effect on the structure of Cu/SBA-15 and nearly pure objective FF product can be feasibly obtained with an appropriate Cu support in the synthesis of FA from FF hydrogenation.
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GREEN CHEMISTRY
·
2025
·
IF 9.2
Yahui Jiang,Haichuan He,Dan Xia,Hongwei Zhang,Shirui Tan,Li Luo,Yifan Kong,Liu Deng,You-Nian Liu
Cu-based catalysts are widely employed in the electrocatalytic CO2 reduction reaction (CO2RR) toward multi-carbon (C2+) products due to their unique electronic structures. However, Cu-based catalysts are prone to reconstruction under working conditions. Self-reduction and undesirable reconstruction have limited the activity and selectivity of these catalysts. Understanding their reconstruction behavior is crucial for elucidating reaction mechanisms and rationally designing catalysts. In this study, Br-doped Cu-base catalysts were employed to investigate the influence of dopants on catalyst surface reconstruction during CO2RR. Characterizations confirmed that during CO2RR, partial Br− leached from the precursor, while residual bromide ions in the Cu matrix created a bromine-rich environment on the catalyst surface, stabilizing Cu0/Cu+ active sites. The reconstructed catalyst exhibited superior selectivity for C2+ products and higher current density. In situ characterization and theoretical calculations demonstrated that the interaction between Br and Cu atoms suppressed complete Cu reduction. Furthermore, the asymmetric coupling pathway via *CO and *CHO intermediates dominated C2+ product formation, with significantly reduced Gibbs free energy of key intermediates compared to undoped CuO. Notably, halogen doping was validated as a universal strategy—Cu–Cl and Cu–F catalysts similarly enhanced C2+ production while exhibiting analogous reconstruction behavior. This study provided deep insights into catalyst surface reconstruction and offered effective strategies for designing high-performance catalysts for CO2RR.
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APPLIED CATALYSIS A-GENERAL
·
2025
·
IF 4.8
Weimeng Cai,Haojie Du,Erju Wang,Yuting Qiang,Kunhong Hu,Jianhua Guo
The synthesis of value-added chemicals from renewable biomass is becoming increasingly important in the transition to a sustainable and low-carbon energy system. Herein, we demonstrate a solvent-polarity modulation strategy to engineer biomass-derived Cu-MOF using 2,5-furandicarboxylic acid (FDCA) as a renewable ligand, where tailored β/α ratios via Kamlet-Taft parameters balance nucleation-growth kinetics to optimize textural properties. Pyrolyzed Cu-MOF at 500 °C under a nitrogen atmosphere yield the Cu/C catalysts, which were subsequently employed in the selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). Among the various solvents used, the Cu-MOF precursor synthesized in a mixed solvent of methanol and N, N-dimethylformamide (DMF) demonstrated the highest catalytic performance, outperforming those synthesized in other solvents. This highlights the significant impact of solvent selection on the structure of Cu-MOF, which in turn affects their hydrogenation activity. Advanced characterization confirming that the uniform Cu dispersion (confirmed by HRTEM mapping) and Cu⁰/Cu⁺ electronic synergy (via Cu Auger analysis) enhanced hydrogenation performance. Additionally, the biomass-derived catalysts exhibited excellent durability. Overall, this research provides a promising approach to develop highly efficient catalysts using renewable ligands and demonstrates the potential of regulating catalyst properties through the strategic selection of solvents, as informed by Kamlet-Taft parameters.
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ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Lixiong Xu,Shuo Geng
Electrocatalytic glycerol oxidation reaction (GOR) coupled with hydrogen evolution reaction (HER) is an ideal method to achieve efficient hydrogen production. However, realizing the stable degradation of glycerol to formate at high current densities still faces great challenges, mainly stemming from the competition between GOR and oxygen evolution reaction (OER) at high potentials. To address this issue, in this study, S–Cu–Ni/NF catalysts were successfully synthesized using Cu–Ni/NF catalysts as precursors. The introduction of Cu effectively suppressed the OER, enabling the catalysts to achieve more than 75% formate Faraday efficiency over a wide potential range from 1.3 V vs RHE to 1.6 V vs RHE. Meanwhile, S doping significantly enhanced the electron transport ability of GOR, enabling the S–Cu–Ni/NF catalyst to achieve a high current density of 100 mA cm–2 at a low potential of 1.395 V vs RHE. In addition, after 24 h of continuous operation at a high current density of 100 mA cm–2, the catalyst potential increased by only 40 mV, demonstrating excellent stability. Scanning electron microscopy with energy dispersive spectra (SEM-EDS), X-ray photoelectron spectra (XPS) and in situ Raman characterization confirmed that the precipitation of S promoted the formation of the active site NiOOH and its dynamic growth during the GOR process. The present study not only improved the selectivity of formate at high potentials by inhibiting OER but also significantly enhanced the GOR performance, demonstrated the potential of stable degradation of glycerol at high current densities, and provided a feasible strategy for the industrial application of glycerol oxidation coupled with hydrogenolysis.
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