INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2024
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IF 8.1
Wei Zhou,Mazhar Ahmed Memon,Mengmeng Niu,Xinqiang Fan,Yanan Jiang,Xian Zhang,Yuan Liu
Copper (Cu) based catalysts are frequently used in CO 2 hydrogenation, particularly in reverse water-gas shift (rWGS) and CO 2 -to-methanol reaction. Cu 0 and Cu + are the key species affecting the catalyst performance and product distribution . Therefore, constructing and adjusting Cu 0 /Cu + active pairs is significant for the catalyst design . In this study, Cu 0 /Cu + active pairs are obtained by utilizing the properties of perovskite-type oxides (PTOs). A series of CaTi 1-x Cu x O 3 and Ca 0.8 La 0.2 Ti 1-x Cu x O 3 (x = 0.05, 0.10, 0.15, 0.30, 0.40 and 0.50) were synthesized via citric acid complexing method and part of the Cu species entered the PTOs lattice. After reduction, large Cu particles and highly-dispersed Cu clusters were obtained simultaneously. The dispersed Cu clusters have more interfaces with the PTOs and provide abundant Cu + while large Cu particles tend to aggregate and supply mainly Cu 0 . Cu 0 activates H 2 and CO 2 and plays a vital role in the rWGS reaction . Cu + is the active site for methanol synthesis and it can strongly absorb CO. The ratio of Cu 0 /Cu + varies with different Cu content and doping La can also adjust the chemical state of surface Cu. The performance test demonstrates that both excessively high and low Cu 0 /Cu + ratios are beneficial for CO generation, while a moderate ratio is suitable for methanol synthesis . These insights provide a method for regulating the chemical state of surface metal species and help the catalyst design for CO 2 hydrogenation.
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LANGMUIR
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2024
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IF 3.7
Yuling Shi,Qing Liu,Qianqian Pan,Danlong Yang,Yangeng Lan,Tao Wang
Nanoparticle composite microspheres are a versatile material with unique features and wide-ranging applications, including catalysis, biological medicine, and electronic devices. The adsorption behavior of nanoparticles on the surface of microspheres plays a crucial role in determining the further application potentials. The understanding of nanoparticle adsorption behavior on microsphere surfaces is essential for guiding future applications in nanoparticle composite microspheres. In this work, the adsorption behavior of unstable copper nanoparticles (Cu NPs) on polystyrene-based (PS-based) microspheres was investigated. The influence of PS-based microspheres’ surface properties and the oxidation degree of Cu NPs were determined. The adsorption mechanism of Cu NPs on PS-based microspheres was analyzed. Furthermore, the amounts and rates of adsorption were examined. It was found that the Cu NPs can be rapidly and firmly adsorbed on the surface of carboxyl-modified polystyrene microspheres. Additionally, precise control over the distribution of Cu NPs on the surface of PS-based microspheres can be achieved by manipulating the solvent’s polarity.
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Nature Communications
·
2024
·Vol. 15
·期 1
·1-14
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IF 14.7
Liu Shikai,Li Yuheng,Wang Di,Xi Shibo,Xu Haoming,Wang Yulin,Li Xinzhe,Zang Wenjie,Liu Weidong,Su Mengyao,Yan Katherine,Nielander Adam C.,Wong Andrew B.,Lu Jiong,Jaramillo Thomas F.,Wang Lei,Canepa Pieremanuele,He Qian
The reconstruction of Cu catalysts during electrochemical reduction of CO 2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO 2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value ( e.g ., −0.4 V RHE when using 0.1 M KHCO 3 ). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO 2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.
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JOURNAL OF ORGANIC CHEMISTRY
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2020
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IF 4.335
Shimin Xie,Lebin Su,Min Mo,Wang Zhou,Yongbo Zhou,Jianyu Dong
An alternative thioesterification reaction via copper-catalyzed oxidative coupling of readily available aroylhydrazides with disulfides is developed, in which oxidative expulsion of N2 overcomes the activation barrier between the carboxylic acid derivatives and the products. The reaction produces various thioesters in good to excellent yields with good functional group tolerance. In the reaction, stable and easily available aroylhydrazides are used as acyl sources and the relatively odorless disulfides are used as S sources. Mechanistic investigations demonstrate that the reaction of copper salt and oxidant (NH4)2S2O8 allows for achievement of tandem processes, including deprotonation, free-radical-mediated denitrogenation, and C–S bond formation.
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ACS Sustainable Chemistry & Engineering
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2026
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IF 7.3
Tao Ding,Shunjie Shu,Yichen Gong,Zhensong Xu,Wen Xu,Jie Zhang,Lei Shi,Hui Sun,Yanhan Chen,Baitao Guo,Yujing Tan,Deliang Xu,Shu Zhang,Shaobin Wang,Hongqi Sun
Biomass waste utilization to produce desirable carbon-based catalysts opens new horizons for achieving carbon neutrality. Nevertheless, efficient manipulation of carbon support morphology and electronic structures of active sites remains a great challenge. By selecting adhesive-contained fiberboard waste as a C/N source and low-cost copper nitrate as a Cu donor, a well-designed carbon catalyst loaded with Cu atomic centers was constructed via a ZnCl2-assisted calcination strategy. Without adscititious N sources, the adhesive contributes to N doping into the carbon framework, further serving as Cu anchoring sites. Meanwhile, ZnCl2 adoption introduces abundant hierarchical pores, significantly improving the available surface area to enhance N doping and Cu dispersion. The as-synthesized catalyst (Cu ACs/aFC) exhibits impressive merits, such as a high specific surface area (∼1222 m2 g–1), homogeneously dispersed Cu sites with robust Cu–Nx configurations and tunable electronic structures, favorable surface hydrophilicity, and excellent electron migration, making it a promising candidate for catalytic reduction of nitroarenes and azo dyes. Taking 4-nitrophenol (4-NP) conversion into a high-value-added chemical (4-aminophenol) as an example, an impressive catalytic performance with a high TOF of 100.26 h–1 (∼2.1-fold that of its counterpart of Cu nanoparticle catalyst), as well as excellent reusability and long-term stability of up to 200 h, is achieved. Particularly, an efficient hydrogenation reduction toward a series of 4-NP analogues and azo dyes is demonstrated, displaying a huge application potential. Through selecting diverse metal precursors, the proposed strategy could be generalized to construct various biochar-based catalysts for advanced hydrogenation reactions.
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APPLIED SURFACE SCIENCE
·
2026
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IF 6.9
Xiaofang Wen,Hongcan Lou,Zheng Li,Jiehao Xie,Zirui Qin,Xingkun Chen,Yuan Tan,Nian Lei,Wei Lu,Yunjie Ding
The development of efficient catalysts for the selective hydrogenation of dimethyl oxalate (DMO) to high-value oxygenates is of great industrial importance. This study presents a systematic investigation into the promotional effect of gallium (Ga) on Cu/SiO 2 catalysts for tailoring product selectivity in DMO hydrogenation. A series of Ga x Cu 30 /SiO 2 catalysts with varying Ga loadings (x = 0.5, 1, 3 wt%) were synthesized via the ammonia evaporation method. With a moderate Ga doping of 0.5 wt%, the Ga 0.5 Cu 30 /SiO 2 catalyst achieved an exceptional ethylene glycol (EG) yield of 74 %, which is three times higher than its Ga-free counterpart (23 %). Further increases in Ga loading to 1 and 3 wt% redirected the reaction pathway, steering the selectivity towards ethanol (ET, 81 %) and 2-methoxyethanol (MT, 54 %), respectively. Characterization by N 2 O titration, XRD, XPS, in situ FT-IR and H 2 -TPR revealed that Ga incorporation fine-tunes the synergy between metallic Cu 0 (for H 2 dissociation) and Cu + sites (for C=O bond polarization). Concurrently, the generated surface acid sites facilitate subsequent dehydration and hydrogenolysis steps. Consequently, the catalytic performance is directly correlated with the evolution of Cu valence states and surface acidity. This work provides a rational strategy for designing multifunctional catalysts for the selective synthesis of target chemicals from DMO.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2026
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IF 9.2
Zezhuang Wang,Yue Lyu,Baihe Guo,Yuchuan Feng,Haiyu Liu,Yan Jin,Juntian Niu
The efficient removal of ultra-low concentration methane from sources like coal mine ventilation air is crucial for mitigating greenhouse gas emissions. This study systematically investigates the effects of synthesis methods (impregnation, combustion, sol-gel, and co-precipitation) and Cu/Co ratios on the catalytic performance of Cu-Co/CeO 2 catalysts for ultra-low concentration methane combustion. Characterization results demonstrate the structural advantages of the optimal catalyst. XRD patterns confirm the successful formation of a CuCo 2 O 4 spinel phase. SEM images show a uniform morphology with minimal agglomeration. XPS analysis further reveals the coexistence of Cu 2+ /Cu + and Co 3+ /Co 2+ redox couples accompanied by abundant adsorbed oxygen species. Experiments demonstrate that the 1Cu-4Co/CeO 2 catalyst prepared by co-precipitation exhibits optimal low-temperature activity, with T 10 and T 90 values of 330 °C and 566 °C, respectively. Stability evaluations over 20 h at 500 °C show minimal activity decay, with the catalyst retaining 94.2% of its initial conversion. The superior performance is attributed to the synergistic redox interaction between Cu and Co, optimized surface oxygen mobility, and robust structural stability. This work provides an effective strategy for designing non-noble metal catalysts for ultra-low concentration methane purification.
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CHEMISTRY OF MATERIALS
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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
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2019
·Vol. 9
·期 71
·41561-41568
·
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
·
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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