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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Biofuel cell assembled by Cu2O nanocube laccase-mimicking nanozyme based sensitive self-powered sensor to detect fungicide thiophanate-methyl

Zhenchao Li,Mingyang Wang,Ying Zhang,Zihan Bian,Xin Liu,Lu Bai,Aihua Liu

Nanozymes exhibit excellent catalytic activity and stability, making them as potential substitutes for natural enzymes with extensive applications in self-powered biosensors (SPB). In this study, Cu 2 O nanocubes (NCs) exhibiting good laccase-like activity were simply synthesized. Subsequently, a two-compartment biofuel cell (BFC) was assembled, consisting of an anodic chamber containing Cu 2 O NCs modified glassy carbon electrode (GCE) anode fueled by catechol, and a cathodic chamber featuring a bilirubin-oxidase/multi-walled carbon nanotubes (MWCNTs)/GCE biocathode. Notably, due to the ethylenediamine-like group in thiophanate-methyl (TM), which has a strong affinity for chelating the Cu(II)/Cu(I) active sites of the laccase-like of Cu 2 O NCs, the formation of Cu N bond leads to a significant inhibition of laccase-like activity and a great reduction in the open circuit potential (OCP) of the BFC. Based on this principle, an SPB was constructed to detect TM. The decline in OCP (ΔOCP) demonstrated a linear relationship with TM concentration ranging from 0.5 to 40 μM, achieving a lower detection limit of 0.11 μM (3σ/S). Moreover, the sensor exhibited no interference from other fungicides, indicating they did not affect TM detection. The as-developed sensor can be applicable to measure TM in soil and seawater samples satisfactorily. Thus, this study casts prospects for the application of nanozymes in self-powered sensors and lays the foundation for the development of fuel cells powered by phenolic pollutants in the future.

CAS / MDL: 120-80-9
研究领域: 生物传感器 · 纳米技术 · 环境监测 · 酶模拟 · 分析化学
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Advanced Science · 2024 · IF 14.3

Synthesis of Closely-Contacted Cu2O-CoWO4 Nanosheet Composites for Cuproptosis Therapy to Tumors With Sonodynamic and Photothermal Assistance

Zhuoran Yang,Zhuo Li,Chunyu Yang,Li Meng,Wei Guo,Liqiang Jing

Cuproptosis offers a promising and selective therapeutic strategy for cancer therapy. To fully realize its potential, the development of novel cuproptosis therapeutic agents and the achievement of efficient copper release are critical steps forward. Herein, closely-contacted Cu 2 O-CoWO 4 nanosheet heterojunctions (CCW-NH) are successfully synthesized using an in-situ process for cuproptosis therapy. The efficient release of copper ions from CCW-NH can be triggered by ultrasound irradiation, primarily due to the generation of superoxide radicals as the sonodynamic agents via the Z-scheme charge transfer mechanism. When subjected to the combined effects of ultrasound and laser irradiation, the effective release of copper ions is increased by 1.7 times compared to the untreated group, significantly enhancing the efficiency of cuproptosis. And the incorporation of CCW-NH and L-arginine into the temperature-sensitive injectable hydrogel (HP-CCW@LA) ultimately achieved a tumor inhibition rate of up to 95.1%. L-arginine, serving as a reducing agent, enabled the sustained release of highly active Cu + during treatment. Notably, after treating tumors with HP-CCW@LA, the tumor microenvironment is leveraged to promote copper ion conversion, which offers the potential for monitoring tumor therapy efficacy through magnetic resonance imaging. This work offers a novel integrated strategy for the development of new cuproptosis agents and therapeutic evaluation.

研究领域: 癌症治疗 · 纳米技术 · 材料科学 · 医学成像
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Nano Today · 2024 · IF 13.2

Synergistic enhancement of ultrahigh SERS activity via Cu2O@Ag Core-Shell structure for accurate label-free identification of breast tumor subtypes

Yujiao Xie,Chao Chen,Chenguang Zhang,Lei Xu,Zihou Li,Wenzhi Ren,Xiawei Xu,Yong Ren,Jie Lin,Aiguo Wu

Conventional methodology for accurate identification of breast tumor subtypes is complex and time-consuming. Label-free SERS (surface-enhanced Raman scattering) enables rapid detection of biomolecules and provides intrinsic fingerprint information of analytes. Exploring reliable SERS bioprobes with high sensitivity and repeatability is essential for efficient typing of cancer cells. In this study, a novel core-shell noble metal-semiconductor Cu 2 O@Ag heterostructure with uniform morphology and outstanding SERS activity for label-free detection has been proposed. The Cu 2 O@Ag SERS substrates exhibit exceptional sensitivity to detect 4 nitrophenthiol (4NTP) at extreme low concentration (10 −15 M), and the SERS spectra demonstrate excellent selectivity and repeatability (RSD ≈ 8.84%). The enhancement mechanism is attributed to the synergistic enhancement of photoinduced charge transfer and boosted surface plasmon resonance effect, confirmed by reduced fluorescence lifetime of methylene blue on SERS substrates and enhanced electromagnetic field intensity via finite-difference time-domain computational simulation. The ultrahigh sensitivity and good signal stability endow Cu 2 O@Ag SERS bioprobe potential for accurate detection of four breast cancer cells subtypes. The rich fingerprint information from SERS spectra is processed using linear differentiation analysis, revealing a high accuracy of 93.3% for subtypes classification. These results demonstrate an excellent SERS bioprobe with high sensitivity and repeatability for precision diagnosis has been developed.

CAS / MDL: 4556-23-4
研究领域: 材料科学 · 生物医学工程 · 癌症研究 · 分析化学
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OPTICS EXPRESS · 2021 ·Vol. 30 ·期 1 ·588-602 · IF 3.894

Double profound enhancements of Cu2O nano-octahedrons connected by intertwined Ag nanovines for elevating SERS activity toward ultrasensitive pesticide detection

Anxin Jiao,Qingqiang Cui,Shuang Li,Yue Tian,Hui Ma,Chang Wang,Mengya Zhang,Ming Chen,Guihua Li,Guihua Li,Xiangdong Liu,Xiangdong Liu

Recently, hybrid plasmonic metal/semiconductor-based surface-enhanced Raman scattering (SERS) has attracted ever-increasing attention due to its combined characteristics of electromagnetic (EM) enhancement and chemical (CM) enhancement, holding great potential for trace molecular detection. Herein, we demonstrate an interesting heterostructure by linking Cu2O nano-octahedrons with intertwined Ag nanovines (NVs). The obtained Ag NVs/Cu2O heterostructures exhibit excellent SERS activity, which is about 2.7 and 7.0 times higher than that of monodispersed Ag or Au nanoparticles (NPs) modified Cu2O. The intertwined Ag NVs among adjacent Cu2O octahedrons serve as efficient electron transport channels, which can obviously promote the separation of electrons and holes, reduce the recombination of photogenerated carriers, and then improve the CM enhancement effect. Meanwhile, the accumulated electrons on plasmonic NVs can effectively optimize the collective oscillation of electrons and further improve the EM enhancement. The optimal SERS substrate possesses fascinating multifunctional SERS properties, including ultra-low detection limit (CV, 10−14 M), excellent anti-interference capability and selectivity. Finally, the established nanosensor can be effectively applied for the quantitative detection of pesticide thiram molecules in soil and biological samples, with low detection limits of 0.48 ng g−1 and 10−7 M, respectively. The proposed work demonstrates a high-performance SERS heterostructure with both improved CM enhancement and enhanced EM effect by linking adjacent Cu2O nano-octahedrons with Ag NVs, which is particularly suitable for ultrasensitive residual pesticide detection in real-world environment.

研究领域: 材料科学 · 纳米技术 · 分析化学 · 环境科学
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CHINESE JOURNAL OF CATALYSIS · 2025 · IF 17.7

Efficient photoelectrochemical cell composed of Ni single atoms/P, N-doped amorphous NiFe2O4 as anode catalyst and Ag NPs@CuO/Cu2O nanocubes as cathode catalyst for microplastic oxidation and CO2 reduction

Hong-Rui Zhu,Xi-Lun Wang,Juan-Juan Zhao,Meng-Han Yin,Hui-Min Xu,Gao-Ren Li

Plastics are ubiquitous in human life and pose certain hazards to the environment and human body. The increasing amount of CO 2 in the atmosphere will lead to the greenhouse effect. Therefore, it is urgent to treat microplastic waste and CO 2 by using environmentally friendly and efficient technologies. In this work, we developed an efficient photoelectrocatalytic system composed of Ni single atoms (Ni SAs) supported by P, N-doped amorphous NiFe 2 O 4 (Ni SAs/A-P-N-NFO) as anode and Ag nanoparticles (Ag NPs) supported by CuO/Cu 2 O nanocubes (Ag NPs@CuO/Cu 2 O NCs) as cathode for microplastic oxidation and CO 2 reduction. The Ni SAs/A-P-N-NFO was synthesized by calcination-H 2 reduction method, and it achieved a Faraday efficiency of 93% for the oxidation reaction of poly (ethylene terephthalate) (PET) solution under AM 1.5 G light. As a photocathode, the synthesized Ag NPs@CuO/Cu 2 O NCs was utilized to reduce CO 2 to ethylene and CO at 1.5 V vs . RHE with selectivity of 42% and 55%, respectively. This work shows that the photoelectrocatalysis, as an environmentally friendly technology, is a feasible strategy for reducing the environmental and biological hazards of light plastics, as well as for efficient CO 2 reduction.

研究领域: 环境科学 · 材料科学 · 电化学 · 纳米技术 · 催化
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TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA · 2016 · IF 1.34

Fabrication of Cu2O@Cu2O core–shell nanoparticles and conversion to Cu2O@Cu core–shell nanoparticles in solution

Ai-ling YANG,Shun-pin LI,Yu-jin WANG,Le-le WANG,Xi-chang BAO,Ren-qiang YANG

Cu 2 O@Cu 2 O core-shell nanoparticles (NPs) were prepared by using solution phase strategy. It was found that Cu 2 O@Cu 2 O NPs were easily converted to Cu 2 O@Cu NPs with the help of polyvinylpyrrolidine (PVP) and excessive ascorbic acid (AA) in air at room temperature, which was an interesting phenomenon. The features of the two kinds of NPs were characterized by XRD, TEM and extinction spectra. Cu 2 O@Cu NPs with different shell thicknesses showed wide tunable optical properties for the localized surface plasmon (LSP) in metallic Cu. But Cu 2 O@Cu 2 O NPs did not indicate this feature. FTIR results reveal that Cu + ions on the surface of Cu 2 O shell coordinate with N and O atoms in PVP and are further reduced to metallic Cu by excessive AA and then form a nucleation site on the surface of Cu 2 O nanocrystalline. PVP binds onto different sites to proceed with the reduction utill all the Cu sources in Cu 2 O shell are completely assumed.

研究领域: 纳米材料 · 无机化学 · 等离子体学 · 胶体化学 · 纳米技术
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APPLIED SURFACE SCIENCE · 2023 · IF 6.7

Boosting the catalytic activity of Cu2O via forming composite with both Cu and metal oxides MO2 (M = Mo and W) by tuning its band structure and Lewis acidity

Yi Pei,Jie Li,Zhaoyang Wang,Wei Zhong,Chunxin Lu,Zhongquan Shen,Nianlong Qian,Xiaoming Liu

In this work, composite materials (Cu-Cu 2 O/MO 2 , M = Mo and W) and their thermally treated form were prepared and characterized by using a variety of spectroscopic techniques (XRD, SEM, HRTEM, XPS and UPS) and cyclic voltammetry. Their catalytic performance on aerobic oxidation of various alcohols under mild conditions was investigated with N-methylimidazole (NMI) and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as the co-catalysts. Of the materials, the thermally treated MoO 2 -based material exhibited the best performance and durability. Compared to Cu-Cu 2 O, the involvement of MO 2 significantly enhances the catalytic activity on the oxidation. Our results suggest that the presence of MO 2 not only raises the energy level of VBM of Cu 2 O which is beneficial to O 2 activation and generates internal electric field pointing to the catalytic center (Cu 2 O) which would accelerate the electron transfer from the substrate to the catalyst through forming heterojunction with both Cu and MO 2 , but also disperses the catalytic center. Further, the Lewis acidity of MO 2 with appropriate strength can bring the substrate closer to the catalytic center via adsorption. But appropriate acidity is essential as easy on–off adsorption is desired in the catalysis. Thermal treatment generates oxidation state VI species of stronger acidity which offsets the effect of the raised VBM energy level.

研究领域: 催化 · 材料科学 · 化学工程 · 物理化学
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Journal of Coatings Technology and Research · 2018 ·Vol. 16 ·期 1 ·25-30 · IF 1.619

Cu2O-clay composites with sub-micrometer-sized Cu2O particles for marine antifouling paints

Li Pengchong,Cai Chao,Long Yuhua,Zhu Tang,Dong Haixia,Zhu Caizhen,Zhao Ning,Xu Jian

Microsized Cu 2 O particles are widely used in tin-free marine antifouling (AF) paints. Because of the enlarged specific surface area, utilization of Cu 2 O particles with smaller sizes is a potential way to improve the AF efficiency and lower the Cu 2 O content. In this paper, the clay, commonly applied as filler in the paint, was previously used to control the concentration of free Cu 2 + during the synthesis of Cu 2 O. With the help of clay, the size of obtained Cu 2 O particles decreased from 750 to 460 nm. It has been shown that the smaller-sized Cu 2 O can work against the marine biofouling with a lower content (15 wt%) compared to the commercial microsized Cu 2 O (40 wt%) in the 260 days of marine AF field tests.

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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Band bending caused by forming heterojunctions in Cu-Cu2O/rGO-NH2 semiconductor materials and surface coordination of N-methylimidazole, and the intrinsic nature of synergistic effect on the catalysis of selective aerobic oxidation of alcohols

Jiamei Ma,Wei Zhong,Langlang You,Yi Pei,Chunxin Lu,Zhiyin Xiao,Zhongquan Shen,Xiujuan Jiang,Nianlong Qian,Xiaoming Liu,Shuhua Zhang

In this work, three materials of Cu-Cu 2 O/rGO-NH 2 -4.4/1, -1/1 and -1/10.4, in which the numeric suffices denote the ratio of Cu/Cu 2 O in the materials, were described and characterized using various analytical techniques including FTIR, XRD, SEM, HRTEM, XPS and Raman spectroscopy. To probe the band structures of these materials, UPS, cyclic voltammetry, and UV–vis reflection spectroscopy were also employed. The formation of heterojunctions in the ternary materials tune their band structures by raising the energy level of valence band maximums (VBMs), inducing an internal electric field (IEF) and an electron accumulation layer (EAL) within the materials. Augment of copper content in the materials can enhance the energy level rising. The coordination of N-methylimidazole (NMI) with Cu 2 O of the materials can also contribute to raising the energy level. The changes in these electronic properties bring about a synergistic effect in selective aerobic oxidation of benzylic alcohols via improving O 2 activation and facilitation of electron transfer between the catalyst and the reactants due to the rising of the energy level of VBM and the formation of IEF.

研究领域: 材料科学 · 催化 · 电化学 · 表面科学
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Molecular Catalysis · 2023 · IF 4.6

Br doping promotes the transform of Cu2O (100) to Cu2O (111) and facilitates efficient photocatalytic degradation of tetracycline

Lianyang Zhang,Yue Meng,Bo Xie,Zheming Ni,Shengjie Xia

The activity of single-crystal catalysts with different crystal faces varies greatly, and the construction of catalysts with highly exposed active facets is essential for the improvement of photocatalytic performance. In this paper, Cu 2 O (100) crystal facets were transformed into high degrade-active Cu 2 O (111) crystal facets by doping with halogen atoms Br for the photocatalytic degradation of tetracycline. The effect of the optimal Br/Cu 2 O ratio on the degradation activity was investigated by adjusting the amount of Br. Meanwhile, based on photocatalytic degradation performance tests, photoelectric performance characterization and theoretical calculations, it was found that the doped Br-Cu 2 O introduced impurity energy levels, reduced the band gap, broadened the absorption range of the photocatalyst under visible light, and enhanced the oxidation capacity and the rate of photogenerated electron leap. In addition, the highly active Cu 2 O (111) crystal surface facilitates the adsorption of oxygen to generate superoxide radicals and promote the photocatalytic reaction. The synergistic effect of these two aspects promotes the efficient degradation of tetracycline by Br-Cu 2 O. This work provides a promising idea for the design and construction of highly efficient active surface highly exposed photocatalysts.

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DALTON TRANSACTIONS · 2021 ·Vol. 50 ·期 26 ·9076-9087 · IF 4.39

Construction of MOF-shell porous materials and performance studies in the selective adsorption and separation of benzene pollutants

Yu Qiao,Na Lv,Dong Li,Hongji Li,Xiangxin Xue,Wei Jiang,Zhanlin Xu,Guangbo Che

Metastable Cu2O is an attractive material for the architectural design of integrated nanomaterials. In this context, Cu2O was used as the sacrificial agent to form the core–shell structure of Cu2O@HKUST-1 by in situ growth technology. The MOFs with BOPs adsorption property were gathered together by a Cu2O etching method, and the hollow structure of the HKUST-1 shell material with fast BOP adsorption was successfully constructed. The adsorption experiments showed that the HKUST-1 shell has a good adsorption effect on nitrobenzene pollutants in wastewater. The investigation of various factors affecting the adsorption, thermodynamic and kinetic equations was carried out. The adsorption equilibrium was reached within 30 min, and the maximum adsorption capacity was 94.67 mg g−1 at 298 K. The adsorption capacity of nitrobenzene by the HKUST-1 shell is in good agreement with the Freundlich model and the second-order kinetic model. The possible mechanism of adsorption of nitrobenzene by the HKUST-1 shell was discussed. The experimental results suggested that Cu-BTC materials have potential applications for wastewater treatment involving benzene pollutants.

研究领域: 材料科学 · 环境科学
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Current Nanoscience · 2022 ·Vol. 18 ·期 1 ·94-105 · IF 1.513

Morphological Changes in Cu2O Nanoshells During Photocatalysis

Ailing Yang,Lele Wang

Background: Semiconductor nanomaterials are being employed for the degradation of organic compounds under solar light irradiation. Introduction: Cu2O nanomaterial is suitable for visible-light photocatalysis because the narrow band-gap (∼2.17 eV) allows it to absorb visible light. However, the morphological changes of Cu2O during photocatalysis have been rarely investigated. Methods: Porous Cu2O nanoshells (NSs) with a nearly 100% hollow structure were synthesized by a two-step addition of reducer. The synthesized NSs were characterized and employed for the photocatalysis of methyl orange (MO) in a neutral solution at 30 °C in air. Results: The Cu2O NSs exhibited high adsorption and good photocatalysis rates with respect to the degradation of MO. Certain new phenomena were observed upon photocatalysis. Nearly all the chemical bonds in MO were fractured; however, a portion of the sulfur-containing group in MO remained on the NSs. The morphology of the Cu2O NSs changed and a large amount of nano-debris was produced. Further experimental analysis indicated the presence of some nano-debris after adsorption- desorption equilibrium (ADE). A negligible amount of nano-debris appeared during the light irradiation of the Cu2O suspension in the absence of MO. The results obtained via X-ray diffraction (XRD), scanning transmission electron microscopy (STEM) and high-resolution transmission electron microscopy (HRTEM) proved that the nano-debris was composed of Cu2O, and essentially comprised nanosheets that were discarded from the Cu2O NSs. Conclusion: The porous NSs were composed of Cu2O nanosheets with exposed {111} facets, which resulted in their strong adsorption ability and catalysis performance for the degradation of MO. Light irradiation accelerated this interaction and led to the discarding of Cu2O nanosheets from the Cu2O NSs. Because of the strong interaction between Cu+ and S, a portion of the sulfur-containing group in MO remained on the NSs after photocatalysis.

研究领域: 纳米材料 · 光催化 · 环境化学 · 材料科学 · 半导体物理
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