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ChemNanoMat · 2021 ·Vol. 7 ·期 3 ·277-283 · IF 3.154

Preparation of Cu(І) Decorated 2D Black Phosphorus Nanosheets for Adsorption Desulfurization from Model Fuel

Jie Wang,Hongqin Ma,Jia Li,Xinyue Luo,Luqi Yu

Graphical Cu(I) decorated 2D black phosphorus nanosheets were synthesized by a ball-milling method . In the process of ball-milling, the bulk black phosphorus was exfoliated into nanosheets under the action of shearing force. Due to the reducibility of black phosphorus, it can react with CuCl 2 to form Cu(I)/BNPSs-n. As the active component of the adsorbent, Cu(I) species can interact with benzothiophene or dibenzothiophene in fuel to achieve the purpose of adsorption desulfurization. In this study, Cu(І) decorated two-dimensional black phosphorus nanosheets (BPNSs) adsorbents were prepared by a ball-milling method, and their adsorption-desorption performances were tested by batch adsorption experiments. The results showed that Cu(ІI) can be completely reduced to Cu(І) without adding any additional reducing agents during the ball-milling process, owing to the ability of black phosphorus to provide electrons to Cu(ІI). Moreover, the produced Cu(І) species were firmly anchored on BPNSs surface through chemical bonds formed between Cu and P atoms, effectively preventing them from aggregating. As the active sites on BPNSs surface, Cu(I) species can adsorb dibenzothiophene or benzothiophene from fuel by forming π-complexation bonds with them. The maximum adsorption capacity of the adsorbent for dibenzothiophene and benzothiophene were 13.16 and 18.02 mg S/g, respectively. Besides, the adsorption desulfurization activity can be recovered well by adopting simple thermal treatment.

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JOURNAL OF MEMBRANE SCIENCE · 2021 · IF 8.742

Self-cleaning loose nanofiltration membranes enabled by photocatalytic Cu-triazolate MOFs for dye/salt separation

Siyu Zhou,Xiaoquan Feng,Junyong Zhu,Qiangqiang Song,Guang Yang,Yatao Zhang,Bart Van der Bruggen

Although membrane separations have evinced an enormous potential in the treatment of dye wastewater, the ubiquitous membrane fouling leads to a dramatic decline of separation efficacy and life span, impeding the progress of membrane-based applications. The copper-triazolate MOFs (CuTz-1) exhibit robust thermal and chemical stability with a unique feature of degrading organic molecules under the visible light, rendering them highly promising for construction of self-cleaning membrane. This study presents the utilization of photocatalytic MOFs (CuTz-1) for construction of the CuTz-1/graphene oxide (CuTz-1/GO) composite membranes via filtration-assisted assembly followed by chemical crosslinking. The presence of CuTz-1 among the GO nanosheets promotes an enhancement of the GO interlayer distance, thereby promoting a higher water flux without compromising the dye rejections. The best-performing CuTz-1/GO membranes exhibits the high water permeance of 40.2 L m −2  h −1 bar −1 and superior dye rejections (Congo red: 99.4%, direct red: 98.2%, methyl blue: 94.9%), low salt rejections (e.g., NaCl: 0.3% and Na 2 SO 4 : 19.6%), as well as long-term nanofiltration stability. Furthermore, after visible light irradiation, the treated membrane was nearly recovered to have the original separation efficacy due to effective photocatalytic removal of the attached dyes from the membrane surface. The CuTz-1/GO membrane also exhibits an ultra-high bacteriostasis rate of 100%, probably to be ascribed to the combined antimicrobial effect of CuTz-1 and GO. This work is expected to give a useful guideline for developing loose nanofiltration membranes with favorable photocatalytic and antimicrobial properties, offering an appropriate solution of using self-cleaning membranes for the treatment of dye wastewater.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2020 · IF 3.99

Laccase-like catalytic activity of Cu-tannic acid nanohybrids and their application for epinephrine detection

Hongchao Ma,Nannan Zheng,Yitong Chen,Lei Jiang

As a green catalyst containing four copper sites in its structure, laccases have attracted considerable research attention and widely applied in pollutant removal, food industry and biosensors. Recently, a series of Cu-based organic-inorganic nanocomposites have been designed as laccase mimics. In this report, we investigated the laccase-like catalytic activity of Cu-tannic acid organic-inorganic nanohybrids (CTNs). Using 2,4-dichlorophenol (2,4-DP) and 4-aminoantipyrine (4-AP) as the substrate, we found CTNs synthesized at low temperature which possessed thin nanostructure and large Cu + /Cu 2+ ratio had higher catalytic activity than those obtained at high temperature. Like natural enzymes as well as other nanozymes, CTNs exhibit pH-dependent catalytic activity and display the optimal catalytic activity in physiological condition. Interestingly, CTNs show high tolerance to temperature and could maintain high catalytic activity even when the temperature was increased to 85 °C. Compared to natural enzymes, CTNs have high stability and excellent recyclability, making them promising candidates in some bio-applications. Moreover, CTNs could catalyze the oxidation of epinephrine to a brown product. Based on this, a simple colorimetric assay for the detection of epinephrine could be constructed.

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INTERNATIONAL JOURNAL OF ENERGY RESEARCH · 2020 ·Vol. 45 ·期 4 ·6273-6284 · IF 3.741

Nanoporous structured Sn-MWCNT/Cu electrodes fabricated by electrodeposition–chemical dezincification for catalytic CO2 reduction

Xiaolin Shao,Qi Zhang,Xurui Zhang,Jin Yi,Yuyu Liu,Jiujun Zhang

Summary A facile method is developed to fabricate nanoporous, structured, Sn-based catalyst electrodes. Sn, Zn, and multiwalled carbon nanotubes (MWCNTs) are co-electrodeposited on a copper substrate, followed by chemical dezincification in NaOH aqueous solution to remove Zn. By controlling variables such as the contents of Zn and MWCNTs, a series of Sn-MWCNT/Cu (S Z MC) electrodes are fabricated. Experimental results show that using such novel S Z MC electrodes can achieve a HCOO − Faradaic efficiency of over 91% at −0.99 V versus RHE for 10 hours in CO 2 -saturated 0.5 M KHCO 3 aqueous solution. The high performance is attributed to the addition of MWCNTs and Zn, followed by chemical dezincification to remove Zn and then create vacancies in the catalyst structure, which results in a special porous structure of S Z MC with large surface area. Then ECSA is used for enhancing the catalytic activity and selectivity of HCOO − production, as well as promoting intermediate adsorption and mass transfer.

CAS / MDL: 7446-20-0
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

In-situ decoration of unsaturated Cu sites on Cu2O photocathode for boosting nitrogen reduction reaction

Ying Liu,Hongye Bai,Qianxiao Zhang,Yajie Bai,Xuliang Pang,Fagen Wang,Yingchen Yang,Jinrui Ding,Weiqiang Fan,Weidong Shi

Photoelectrochemical N 2 reduction reaction (PEC NRR) into chemical energy source is a promising technique for solving environmental challenges and the energy crisis, which depends on the exploration of p-type photocathodes. Cu 2 O is a p-type semiconductor, which can be applied as a photocathode for PEC NRR. However, the adsorption and activation ability of N 2 over the pristine Cu 2 O is still not ideal, causing the overall efficiency far below the theoretical value. In this work, we first proposed a feasible strategy to in-situ modify the surface of Cu 2 O with Cu-MOF, and the Cu-MOF/Cu 2 O heterostructure exhibited the significantly boosted NH 3 production rate (7.16 mmol/m 2 /h). The ultra-thin Cu-MOF film takes a nature of porous structure and unsaturated Cu sites, contributing to a favorable interface environment for the adsorption and activation of N 2 . The N 2 temperature programmed desorption and contrast photocurrent curves revealed the desirable selectivity for PEC NRR, and the isotope NMR further confirmed the accuracy of NH 3 evolution process. Therefore, the organic–inorganic hybrid systems built from Cu-MOF and Cu 2 O would offer a new insight for establishing the efficient PEC NRR system.

CAS / MDL: 554-95-0
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Peptide Science · 2020 ·Vol. 113 ·期 2 ·e24208 · IF 1.865

Self-assembly of hairpin peptides mediated by Cu(II) ion: Effect of amino acid sequence

Jiqian Wang,Chengdong Wang,Yanqing Ge,Yawei Sun,Dong Wang,Hai Xu

The alteration of amino acid register in peptides could affect their folding properties and thus functions. The effect of sequence in metal ion induced folding of peptide/protein is important in the design of new functional protein structures, such as biomimetics. In this paper, a set of hairpin peptides with identical composition but different histidine locations have been designed to exploit the metal ion-mediated peptide intramolecular folding transformation through the adjustment of histidine and lysine residue locations. The results demonstrated that the histidine positions in peptide sequence could dramatically affect the coordination modes between peptides and Cu(II) ion. The Cu(II) coordination could affect the secondary structure transformation and self-assembly along with electrostatic interaction and hydrogen bonding synergistically. Three molecules with VHVH sequence at each side of the turn segment (V D PPT) were apt to coordinate with Cu(II) ion with three or four histidines. The closer the VHVH motifs were to the turn segment, the more easier the molecules were to form β sheet structure with the promotion of Cu(II) ions. These results demonstrated that the purposeful location of key amino acids in peptides could achieve the controllable conformation transformation of hairpin peptides, which provides useful strategies for biomimetic design, such as metalloenzymes. Graphical

CAS / MDL: 4432-31-9
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BIOSENSORS & BIOELECTRONICS · 2020 · IF 10.257

High-performance field-effect transistor glucose biosensors based on bimetallic Ni/Cu metal-organic frameworks

Bingfang Wang,Yuanyuan Luo,Lei Gao,Bo Liu,Guotao Duan

Accurate detection of glucose is essential for the diagnosis of diabetes, wherein effective and sensitive biosensors for glucose detection are needed. Here, we fabricated a glucose sensor based on field-effect transistor (FET) with bimetallic nickel-copper metal-organic frameworks (Ni/Cu-MOFs) as its channel layers which were grown in-situ through a simple one-step hydrothermal method and modified with glucose oxidase (GOD) by using glutaraldehyde (GA) as linkers. Due to the synergistic effect of Ni ions and Cu ions in MOFs, the sensor (GOD-GA-Ni/Cu-MOFs-FET) showed good field effect performance and great responses to glucose through enzymatic reactions . It displayed a piecewise linear relationship in the wide range (1 μM–20 mM), and provided high sensitivity (26.05 μAcm −2 mM −1 ) in the low concentration (1–100 μM) and a low detection limit (0.51 μM). The sensor also had these advantages of high specificity, excellent reproducibility, good short-term stability and fast response time. Especially, it is indicated that the Ni/Cu-MOFs-FETs with high performance have the potential to be available sensors, paving the way for the application of bimetallic MOFs in biosensing.

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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2021 · IF 5.816

Hydrogen adsorption performance of Cu-BTC/graphene aerogel composite: A combined experimental and computational study

Wen Ren,Xudong Zhuang,Zhilu Liu,Song Li

Metal-organic frameworks (MOFs) are reported as potential hydrogen storage materials due to ultrahigh surface area and pore volume . However, most top-performing MOFs for hydrogen storage require strict synthesis conditions and high cost, which limits their wide applications. In this work, Cu-BTC/graphene aerogel (GA) composite is prepared at room temperature with improved hydrogen uptake at 100 bar compared with pristine Cu-BTC. To understand the mechanism of the enhanced hydrogen uptakes in the composite, grand canonical Monte Carlo (GCMC) simulation is executed for Cu-BTC/GA composites with different numbers of graphene oxide (GO) layers. It is demonstrated that the increased hydrogen uptake in Cu-BTC/GA composites is mainly ascribed to the hydrogen uptake in the interface region between Cu-BTC and GA. Additionally, the hydrogen uptake of the Cu-BTC/GA composites decreases as the number of GO layers increases, implicating that fewer GO layers or thinner GA is favorable for hydrogen adsorption of Cu-BTC/GA composites.

CAS / MDL: 7782-42-5 554-95-0
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Energy Technology · 2020 ·Vol. 8 ·期 7 ·1901392 · IF 3.404

Cu/Cu2O Nanoparticle–Decorated MoO2 Nanoflowers as a Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction

Jing Tong,Yanan Xue,Jianzhi Wang,Miao Wang,Weimin Chen,Qifeng Tian,Faquan Yu

The development of highly efficient, economical, and sustainable electrocatalysts based on non-noble metals for hydrogen evolution reaction (HER) is of vital significance for large-scale renewable energy storage. Herein, an effective synthetic strategy for the construction of MoO 2 nanoflowers decorated with metallic Cu/Cu 2 O nanoparticles (NPs) on Ni foam (NF) (Cu 2 O/MoO 2 @Cu/NF) with a simple two-step method is reported. The prepared Cu 2 O/MoO 2 @Cu/NF as an electrocatalyst exhibits outstanding reactivity and remarkable stability in alkaline solution. The onset overpotential of Cu 2 O/MoO 2 @Cu/NF approaches 0 V. An overpotential as low as 32 mV is obtained to afford a current density of 10 mA cm −2 , comparable with Pt/C catalysts. The Tafel slope is low at 40 mV dec −1 as well. The involvement of zero-valent Cu greatly reduces the resistance. The well-dispersed Cu/Cu 2 O NPs on the sphere-like MoO 2 nanoflowers exaggerate the surface area. The ringent channels provide the fast release of evolved bubbles. Furthermore, the enhanced conductivity and large surface area lead to significant activity in HER. Herein, a novel design and facile synthesis of a highly efficient electrocatalyst with catalytic activity that is comparable to a Pt/C catalyst is provided.

CAS / MDL: 7647-01-0
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Environmental Technology & Innovation · 2020 · IF 3.356

Hydrated titanium oxide nanoparticles supported on natural rice straw for Cu (II) removal from water

Yiliang Chen,Hao Shi,He Guo,Chen Ling,Xinyu Yuan,Pingping Li

This study combined agricultural waste utilization with wastewater treatment and developed a novel nanocomposite adsorbent for Cu 2 + 2+ removal from water. Rice straw (RS) was used as the supporter of hydrated titanium oxide (HTO), which has strong affinity toward heavy metals. HTO nanoparticles were uniformly loaded onto the surface of natural rice straw through a facile sol–gel method. The characterization results show that the diameter of the RS-HTO nanoparticles was about 80 nm with SEM. The fabricated nanocomposite RS-HTO exhibited excellent structural stability under different solution pH and ionic strength. Adsorption of Cu 2 + 2+ increased as pH rose from 2.0 to 7.5 with 2 g/L RS-HTO in 50 mL solution (10 mg/L). Meanwhile, when initial concentration of Cu 2 + 2+ was 10 mg/L, the adsorptive removal efficiency was higher than 99% by RS-HTO at a pH level of 7.5. The adsorption selectivity was investigated and proved that the coexisting cation ions such as Na + + , Mg 2 + 2+ and Ca 2+ led to a small decrease of Cu 2 + 2+ adsorption capacity. Adsorption isotherms of Cu 2 + 2+ onto RS-HTO fitted well with Langmuir equation, and the adsorption kinetics were best described by pseudo-second order model. The concentration of Cu 2 + 2+ in the simulated wastewater can be reduced to be lower than 0.2 mg/L through fixed-bed adsorption process and the exhausted RS-HTO can be easily regenerated with HCl–NaCl mixed solution.

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Journal of Materials Chemistry A · 2020 ·Vol. 8 ·期 7 ·4062-4072 · IF 11.301

A graphene oxide–molecular Cu porphyrin-integrated BiVO4 photoanode for improved photoelectrochemical water oxidation performance

Chunjiang Xu,Wanjun Sun,Yinjuan Dong,Congzhao Dong,Qiyu Hu,Baochun Ma,Yong Ding

Monoclinic bismuth vanadate (BiVO4), as a rising star in light-catching materials, has been researched in many fields, such as photoelectrochemical water splitting. To date, it is still noteworthy that the photogenerated electron–hole fast recombination and the slow kinetic rate impede the photoelectrochemical performance of BiVO4. Herein, a composite material of graphene oxide (GO) and molecular Cu porphyrin (CuTCPP)-modified BiVO4-based photoanode was prepared and characterized by various relevant physical tests. The photoelectrochemical performance measurements show that the assembled CuTCPP/GO/BiVO4 photoanode has an admirable photocurrent density value, which is far better than that of pristine BiVO4. Under AM 1.5G, 100 mW cm−2 Xe lamp, the photocurrent density of the CuTCPP/GO/BiVO4 photoanode reached 5.0 mA cm−2, which was 4-fold enhancement than that of pristine BiVO4. In addition, the optimized CuTCPP/GO/BiVO4 photoanode displays an evident negative shift of the onset potential of around 400 mV, and it presents a fascinating charge injection efficiency of 92%. The fine photoelectrochemical performance is due to more active sites provided by the molecular catalyst CuTCPP and excellent electrical conductivity and fast charge separation rate offered by GO. Furthermore, GO and CuTCPP form strong conjugate systems, which effectively inhibit the photogenerated electron–hole recombination. These results offer a new concept of assembling a composite photoanode for efficient energy devices.

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JOURNAL OF CONTROLLED RELEASE · 2020 · IF 7.727

Co-delivery of Cu(I) chelator and chemotherapeutics as a new strategy for tumor theranostic

Tao Sun,Guangping Zhang,Zhongyuan Guo,Qinjun Chen,Yujie Zhang,Yongchao Chu,Qin Guo,Chao Li,Wenxi Zhou,Yiwen Zhang,Peixin Liu,Hongyi Chen,Haijun Yu,Liping Jiang,Chen Jiang

Chelating Cu from tumors has been verified as an effective and promising strategy for cancer therapy through antiangiogenesis. However, systematic removal Cu by injecting with Cu chelators will result unavoidable side effects, since Cu is indispensable to the body. In this work, a micelle targeting to tumors' newborn vessels based on a polypeptide was developed to co-load DOX and Probe X, which can go through an “OFF-to-ON” procedure to report the Cu + -capture events in vivo in a real-time way by giving near infrared (NIR) fluorescence and photoacoustic signal. By co-delivering antiangiogenesis and chemotherapeutic reagents, the tumor can be significantly suppressed, meanwhile with a low systematic toxicity. Hopefully, this work can offer new insights in designing sophisticated antitumor strategy.

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