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Materials Today Communications · 2023 · IF 3.8

Cu-MOFs derived three-dimensional Cu1.81S@C for high energy storage performance

Yanan Chen,Yuanbo Zhao,Weijun He,Yanan Liu,Hongna Xing,Xiuhong Zhu,Yanqun Guo,Juan Feng,Chunyan Liao,Yan Zong,Xinghua Li,Xinliang Zheng

Significant volume changes and slow ionic transport during charge/discharge processes restrict the improvement of electrochemical performance for Cu x S (x = 1–2). Herein, a new strategy by introducing Cu-BTC (copper(II)-benzene-1,3,5-tricarboxylate) as a processor to derive three-dimensional Cu 1.81 S@C using green sulfurization and calcination methods is proposed. Benefiting from the high electrical conductivity , multistage pore size structure and stable structure brought by the conductive carbon skeleton after calcination , Cu 1.81 S@C-650 o C exhibits a high specific capacitance of 291.1 F g -1 at a current density of 1 A g -1 and a superior rate capability of 83.6 % at a current density of 10 A g -1 . In addition, the assembled asymmetric supercapacitor (Cu 1.81 S@C-650 o C//AC ASC) also shows impressive performances, such as an energy density up to 16 Wh kg -1 at a power density of 352 W kg -1 and an excellent cycling stability of 93.1 % over 5000 cycles at a current density of 2 A g -1 . This work demonstrates that the Cu-BTC-derived Cu 1.81 S@C is an attractive material with potential applications in energy storage devices.

研究领域: 材料科学 · 能量存储 · 超级电容器 · 金属有机框架(MOFs) · 纳米材料
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ACS Applied Nano Materials · 2024 · IF 5.3

Enhanced Photothermal and Chemodynamic Tumor Therapy by a Cu–Ca-Based Nanoplatform

Minqin Huang,Erhao Wang,Xiuju Li,Zhiying Wei,Tiantian Wang,Ao Wang,Li Yang

In this study, a fascinating nanoplatform, possessing fluorescent imaging, hyperthermia-amplified reactive oxygen species (ROS) generation, and calcium-overloaded comediated multimodal therapeutic effects toward breast malignancy, was innovatively constructed. Accordingly, engineering this accurate targeting theranostic scheme can be used for efficacious ablation of breast carcinoma. Because Cu and Ca ions can induce ROS generation and cytoplasmic overaccumulation, respectively, here, a Cu–Ca-based nanoplatform was designed by adsorbing indocyanine green (ICG) through the relatively high specific surface area and Arg-Gly-Asp peptide (RGD) decorating by covalent conjugation. Upon the internalization of breast tumor cells, biodegradation was triggered under an intracellular weak acid microenvironment; the released ICG molecules allowed for near-IR (NIR) II fluorescent imaging and photothermal production. Importantly, Cu ions in the nanoplatform guaranteed more efficient Fenton-like reaction-mediated chemodynamic therapy under NIR laser exposure. Meanwhile, the virus-like hollowed Cu–Ca (VhCu-Ca) nanoplatform created an artificial calcium-overloading stress in the cytoplasm. In vitro and in vivo studies have demonstrated that our proposed Cu–Ca-based nanoplatform integrated the advantages of breast tumor targeting, NIR II fluorescent imaging, and efficient ablation via synergistic treatments. Therefore, this multimode nanoplatform developed a facile and versatile strategy for the diagnosis and suppression of breast tumors.

研究领域: 纳米医学 · 癌症诊疗一体化 · 生物医学工程 · 活性氧研究 · 光热治疗
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Journal of Environmental Chemical Engineering · 2022 · IF 7.968

Adsorptive desulfurization using Cu+ modified UiO-66(Zr) via ethanol vapor reduction

Yan Yin,Yueyang Xu,Konglu Guo,Peng Zhang,Yongping Zeng

Adsorptive desulfurization is one of the alternative technologies for the effective removal of sulfides from fuels. Functionalization of metal-organic frameworks (MOFs) with Cu + is extremely desirable for adsorption separation via π-complexation interaction with adsorbed molecules. Here we report that Cu + cation is significant and highly effective for adsorption desulfurization in a new type of Cu + - modified UiO-66(Zr). First, Cu 2+ was introduced via ion-exchange with H + of UiO-66-SO 3 H. Then, Cu + cation was obtained from the reduction of Cu 2+ by using vapor-induced reduction, in which vapors of reducing agents diffuse into the pores of MOFs at a lower temperature. The resulted UiO-66-SO 3 Cu(I)− 0.15 has a better adsorption capacity for thiophene compared to pure UiO-66. In the presence of toluene, the UiO-66-SO 3 Cu(I)− 0.15 also exhibits high adsorption capacity for thiophene. After recycling four times, UiO-66-SO 3 Cu(I)− 0.15 still remains a high adsorption capacity.

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TOPICS IN CATALYSIS · 2023 ·Vol. 66 ·期 19 ·1527-1538 · IF 3.6

Highly Ethylene-Selective Electroreduction CO2 Over Cu Phosphate Nanostructures with Tunable Morphology

Zhang Li,Men Yong,Wu Bin,Feng Yuanfen,Song Chao,Liu Shuang,Wang Jinguo,An Wei,Magkoev Tamerlan T.

Highly selective production of valuable ethylene from electrocatalytic CO 2 reduction reaction (ECO 2 RR) is particularly desirable yet challenging. Morphology engineering is an effective strategy for catalyst design, which can adjust the electronic structure of catalyst surface, change the adsorption behavior of critical reaction intermediates over catalyst surface, and thus regulate the activity of electrocatalytic CO 2 reduction reaction. In this work, we prepared copper phosphate catalysts with different morphologies and tested their catalytic activity for the ECO 2 RR in the flow cell. Compared with irregular flocculent aggregates, copper phosphate nanospheres exhibit a high and stable ethylene Faradaic efficiency of 47% with high current density of 350 mA·cm − 2 , which is higher than the 200 mA·cm − 2 required for industrial applications. The catalysts were extensively characterized by SEM, EDS, XRD, ICP-OES, XPS, BET and CO-TPD. Combining the characterization results and activity data, we found that the superior spherical morphology of copper phosphate can increase the electron density around Cu, stabilize the Cu + species on the surface through the electron transfer between P and Cu, and adjust the adsorption strength of CO intermediates (*CO) to enhance the productivity of C 2+ products. This work provides new insights into catalyst design for highly efficient C 2 H 4 production from the electrocatalytic CO 2 reduction reaction by tuning morphologies of Cu-based catalysts.

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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Synergistic trimetallic Ni–Cu–Sn catalysts for efficient selective hydrogenation of phenylacetylene

Wei Chen,Huawu Xu,Xiaoling Ma,Lin Qi,Zhiming Zhou

Selective hydrogenation of phenylacetylene is the most effective way to remove a small amount of phenylacetylene from styrene, but it is still a challenge to develop catalysts with high activity and selectivity. Herein, a series of non-precious bimetallic Ni 3 M/SiO 2 (M = Zn, Sn, Cd, Fe, Co, Cu, or Mo) and trimetallic Ni 3 Cu–Sn/SiO 2 catalysts were prepared and applied to selective hydrogenation of phenylacetylene. A trade-off between activity and selectivity was observed on Ni 3 M/SiO 2 , where Ni 3 Cu/SiO 2 showed the best hydrogenation activity because of the hydrogen spillover effect of the Ni–Cu alloy, while Ni 3 Sn/SiO 2 exhibited the highest selectivity to styrene due to the active-site isolation effect of the Ni–Sn alloy. Impressively, trimetallic Ni 3 Cu–Sn/SiO 2 offered superior catalytic performance (94 % styrene selectivity at >99 % phenylacetylene conversion) as compared to bimetallic catalysts, owing to the synergistic effect among Ni, Cu, and Sn. In the case of Cu and Sn co-doping, the hydrogen spillover on the Ni–Cu alloy was deeply suppressed by Sn, which enabled an effective modification of the geometric and electronic structures of Ni to favor styrene desorption. The hydrogenation activity of Ni 3 CuSn 0.3 /SiO 2 can be readily enhanced by increasing the metal loading and further improved by elevating the reaction temperature and pressure, but meanwhile the high selectivity is little affected. This work demonstrates a multi-metal synergistic strategy to break the activity–selectivity trade-off of Ni-based bimetallic catalysts in the selective hydrogenation of alkynes.

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JOURNAL OF HAZARDOUS MATERIALS · 2022 · IF 14.224

Cu/Al2O3 aerogels for high-efficiency and rapid iodide elimination from water

Xinyu Zhou,Pin Mao,Huiran Jin,Wanxia Huang,Aotian Gu,Kaiwei Chen,Shan Yun,Jing Chen,Yi Yang

Cu-based functional materials are excellent candidates for the elimination of iodine anions. However, the low utilization rate of Cu and its unsatisfactory adsorption performance limit its large-scale practical applications. This paper proposes a co-gelation method to obtain Cu/Al 2 O 3 aerogels with a high specific area (537 m 2 /g). Cu/Al 2 O 3 aerogels have a hierarchical porous structure and contain a high proportion of Cu (20.5 wt%). The high dispersibility of Cu, which is based on an in-situ gel process, provides conditions for the high-efficiency elimination of iodide anions. We conducted adsorption experiments that demonstrated that the fabricated Cu/Al 2 O 3 aerogel had an ultrahigh adsorption capacity (407.6 mg/g) and a fast adsorption equilibrium time (0.5 h) for iodide anions. Additionally, the Cu/Al 2 O 3 aerogel could selectively capture iodine anions even in the presence of high concentrations of competing ions (NO 3 - , SO 4 2- , and Cl - at 60 mmol/L). Importantly, the aerogel can operate in a wide pH range of 3–11 without causing secondary pollution. This work demonstrates that low-cost Cu/Al 2 O 3 aerogels exhibit great potential for eliminating radioactive iodine anions.

CAS / MDL: 7681-82-5
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EcoMat · 2023 ·Vol. 5 ·期 5 ·e12334 · IF 14.6

Facile design of oxide-derived Cu nanosheet electrocatalyst for CO2 reduction reaction

Juhee Jang,Shangqian Zhu,Ernest Pahuyo Delmo,Tiehuai Li,Qinglan Zhao,Yinuo Wang,Lili Zhang,Hongwen Huang,Jingjie Ge,Minhua Shao

Despite of superior performance of the oxide-derived copper (OD-Cu) in producing valuable hydrocarbons during CO 2 RR, its fabrication process is still ambiguous and complicated. In this work, we develop a simple microwave-assisted method to synthesize the oxide-derived Cu nanosheet (OD-Cu NS) and reveal that the oxidation state of Cu species is controlled by varying the Cu precursor amount. Notably, the simultaneous formation of nano-sized Cu domains influence the surface roughness of OD-Cu NS. The partially oxidized Cu surface exhibits a superior faradaic efficiency (FE) of C 2+ products up to 72%, along with a partial current density of 55 mA cm −2 in a neutral KHCO 3 solution. More importantly, the as-obtained OD-Cu NS shows a synergetic effect on dissociating of CO 2 molecules by the strong binding energy and promoting of C 2+ compounds productivity by the enlarged electrochemical surface area. This work provides a new insight for designing efficient OD-Cu catalysts toward CO 2 RR.

CAS / MDL: 10031-43-3
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Frontiers in Bioengineering and Biotechnology · 2023 · IF 5.7

Multi-stimuli responsive Cu-MOFs@Keratin drug delivery system for chemodynamic therapy

Du Jinsong,Chen Guanping,Yuan Xinyi,Yuan Jiang,Li Li

Although the potential of metal-organic framework (MOF) nanoparticles as drug delivery systems (DDS) for cancer treatment has been established by numerous studies, their clinical applications are still limited due to relatively poor biocompatibility. We fabricated a multifunctional Cu-MOFs@Keratin DDS for loaded drug and chemodynamic therapy (CDT) against tumor cells. The Cu-MOFs core was prepared using a hydrothermal method, and then loaded with the anticancer drug DOX and wrapped in human hair keratin. The Cu-MOFs@Keratin was well characterized by transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), and X-ray photoelectron spectroscopy (XPS). Characterization and pharmacokinetic studies of Cu-MOFs@Keratin were performed in vitro and in vivo. The keratin shell reduced the cytotoxicity and potential leakage of Cu-MOFs to normal cells, and allowed the drug-loaded nanoparticles to accumulate in the tumor tissues through enhanced permeability and retention effect (EPR). The particles entered the tumor cells via endocytosis and disintegrated under the stimulation of intracellular environment, thereby releasing DOX in a controlled manner. In addition, the Cu-MOFs produced hydroxyl radicals (·OH) by consuming presence of high intracellular levels of glutathione (GSH) and H2O2, which decreased the viability of the tumor cells.

CAS / MDL: 69-78-3 70-18-8
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Insights into Electrocatalytic Nitrate Reduction to Ammonia via Cu-Based Bimetallic Catalysts

Jing Zhao,Lijuan Liu,Ya Yang,Dan Liu,Xiaobo Peng,Shijing Liang,Lilong Jiang

Cu-based bimetallic catalysts have been studied in the electrocatalytic nitrate (NO3–) reduction reaction (NO3–RR) for a long time. However, few studies have focused on horizontal comparison of CuNi, CuCo, and CuFe (abbreviated as CuM) bimetallic catalysts in electrocatalytic NO3–RR for ammonia synthesis. Herein, we prepare the three series of Cu-based bimetallic catalysts, with different atom ratios of Cu/M (Cu/M = 7/3, 5/5, or 3/7) and ordered mesoporous carbon (OMC) as support (denoted as CuM/OMC). The characterization results reveal that the metallic particles of Cu and M components possess an intimate relationship on the CuM/OMC catalysts. The electrocatalytic NO3–RR performance uncovers that the optimal NH3 yield rates of CuM/OMC catalysts at −0.8 V (vs reversible hydrogen electrode (RHE)) follow this order: Cu5Fe5/OMC > Cu5Co5/OMC > Cu7Ni3/OMC > Cu/OMC > Fe/OMC > Co/OMC > Ni/OMC > OMC. The bimetallic CuM/OMC catalysts exhibit higher NH3 yield rates than the monometallic catalysts. This is attributed to strong synergistic effects between the Cu and M components. We expect that these insights can stimulate new developments of bimetallic catalysts in electrocatalysis.

CAS / MDL: 9003-11-6
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2022 · IF 24.319

A CuZn-BTC derived stable Cu/ZnO@SiO2 catalyst for ethanol dehydrogenation

Haolan Liu,Zhili Chang,Jie Fu,Zhaoyin Hou

Cu-based catalysts play pivotal role in many industrial processes, however, its application under high temperature is restricted due to the low Tammann temperature of Cu. Improving the stability and activity of Cu-based catalysts at high temperature is a challenge. In this work, a stable Cu/ZnO@SiO 2 catalyst was prepared, in which silicon was introduced into CuZn-BTC precursor via a steam-assisted hydrolysis method before calcination and reduction. Characterizations found that Cu/ZnO@SiO 2 catalyst prepared via above strategy possesses increased surface area, more exposed active sites and excellent stability for ethanol dehydrogenation than Cu/ZnO (prepared from CuZn-BTC without SiO 2 ). It was confirmed that the space-time yield of acetaldehyde reached 9.0 g-acetaldehyde/g-cat/h, and Cu/ZnO@SiO 2 could maintain its activity within 200 h at 350 °C due to the ZnO decorated Cu particles (Cu/ZnO) were encapsulated in the octahedral shaped SiO 2 hollow.

CAS / MDL: 78-10-4
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2022 · IF 24.319

Hierarchical Ag-Cu interfaces promote C-C coupling in tandem CO2 electroreduction

Zhizhou Cai,Ning Cao,Fanxing Zhang,Xiangzhou Lv,Ke Wang,Yi He,Yao Shi,Hao Bin Wu,Pengfei Xie

Electrocatalytic CO 2 reduction into ethanol driven by renewable energy represents a promising strategy for energy storage and mitigation of global warming, but it has remained challenging to gain high activity and selectivity of ethanol. Here we take advantage of atomic arrangement in immiscible Ag-Cu composite during annealing and establish hierarchical interfaces in the obtained core-shell catalyst. The atomic Ag-Cu interactions increase electrochemical surface area and expedite charge dynamics, resulting in an unprecedented electrocatalytic performance with the faradaic efficiency of C 2+ products, ethanol as 80.2 %, 52.6 % and the current density of ∼320 mA cm −2 at −1.0 V (versus reversible hydrogen electrode). Moreover, the Ag-Cu catalyst exhibits a notable stability for ∼60 h. Mechanism studies reveal that local CO intermediates preferentially accumulate on the core, then migrate to the continuous Cu surface for C-C coupling energy-favorably toward ethanol. Our work highlights a novel design principle as interface engineering for advanced tandem electrocatalysts.

CAS / MDL: 25249-54-1 9003-39-8
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2022 ·Vol. 23 ·期 22 ·14072 · IF 6.208

Bioinspired Pd-Cu Alloy Nanoparticles as Accept Agent for Dye Degradation Performances

Shiyue Chen,Yujun Yang,Mingjun Zhang,Xiaohong Ma,Xiaoxiao He,Teng Wang,Xi Hu,Xiang Mao

Dye degradation is a key reaction in organic decomposition production through electron donor transferring. Palladium (Pd) is the best-known element for synthesis Pd-based catalyst, the surface status determines the scope of relative applications. Here we first prepare Pd-Cu alloy nanoparticles (NPs) by co-reduction of Cu(acac)2(acac = acetylacetonate) and Pd(C5HF6O2)2in the presence of sodium borohydride (NaBH4) and glutathione (GSH). The obtained Pd-Cu is about ~10 nm with super-hydrophilicity in aqueous mediums. The structural analysis clearly demonstrated the uniform distribution of Pd and Cu element. The colloidal solution keeps stability even during 30 days. Bimetallic Pd-Cu NPs shows biocompatibility in form of cell lines (IMEF, HACAT, and 239 T) exposed to colloidal solution (50 µg mL−1) for 2 days. It shows the catalytic multi-performance for dye degradation such as methyl orange (MO), rhodamine B (RhB), and methylene blue (MB), respectively. The as-synthesized nanoparticles showed one of the best multiple catalytic activities in the industrially important (electro)-catalytic reduction of 4-nitrophenol (4-NP) to corresponding amines with noticeable reduced reaction time and increased rate constant without the use of any large area support. In addition, it exhibits peroxidase-like activity in the 3, 3′, 5, 5′-Tetramethylbenzidine (TMB) color test and exhibit obvious difference with previous individual metal materials. By treated with high intensity focused ultrasound filed (HIFU), Pd-Cu NPs might be recrystallized and decreased the diameters than before. The enhancement in catalytic performance is observed obviously. This work expedites rational design and synthesis of the high-hierarchy alloy catalyst for biological and environment-friendly agents.Keywords:Pd-Cu NPs;hydrophilic;biocompatibility;catalytic agent;dye degradation

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