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ChemistrySelect · 2024 ·Vol. 9 ·期 44 ·e202403927 · IF 1.9

Photocatalytic Reduction of CO2 by Multimetallic 2D MOF-Co/Cu/Fe

Hui Han,He Cui,Jiabo Wang,Kai Ge,Yongfang Yang

Graphical In this paper, 2D MOF-Co, 2D MOF-Co/Cu, and 2D MOF-Co/Cu/Fe are designed and prepared using 1,4-benzendicarboxylic acid (1,4-BDC) as organic ligands. Their charge transfer, separation efficiency, and effects on photocatalytic CO 2 reduction are studied. The results show that 2D multimetallic MOF-Co/Cu/Fe has better photocatalytic CO 2 reduction activity, so it has higher research value and development prospect in the field of photocatalytic CO 2 reduction. In this study, 2D multimetallic MOFs combined with the advantages of 2D nanosheets, with the synergetic effect of multimetallic nodes, exhibited good photocatalytic activity for reduction of CO 2 . Herein, a 2D MOF-Co/Cu/Fe were successfully prepared via one-pot stirring of the solutions of multimetal salts and organic ligands at room temperature. Introduction of the second and third metal (Cu and Fe) into MOF-Co does not change the 2D morphology of MOFs, although it improved the photocatalytic CO 2 reduction performance by broadening the light absorption range of 2D MOF-Co, accelerating the separation efficiency and transfer rate of photogenerated carriers. Upon irradiation with full-spectrum light, the average CO yield of 2D MOF-Co/Cu/Fe achieved 17.06 µmol·g −1 ·h −1 , being about 1.8 and 1.2 times that of 2D MOF-Co and 2D MOF-Co/Cu. This work provides an insight into 2D multimetallic MOFs-based photocatalysts in catalytic CO 2 reduction.

CAS / MDL: 10026-22-9
研究领域: 材料科学 · 环境科学 · 化学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

Rational design of BiOBr/Ov-TiO2-Cu photocatalyst for efficient nitrogen reduction to ammonia

Ping Li,Huanhuan Wu,Chengming Zhang,Quangui Liang,Huihui Ding,Haibao Zhu,Jun Ma,Xiang Li,Shuangshuang Huai,Congliang Cheng,Xiufang Wang

The lack of active sites and the low availability of photoelectrons severely limit the photocatalytic reduction of nitrogen to ammonia in semiconductor materials. Here, we successfully designed a BiOBr/O v -TiO 2 -Cu heterojunction catalyst toward N 2 fixation into NH 3 . The optimized BiOBr/O v -TiO 2 -Cu heterojunction has a promising photocatalytic performance and stability with the highest NH 3 yield of 259.82 μmol·g −1 ·h −1 . The combination of detailed theoretical simulation calculations and comprehensive characterizations indicates the BiOBr/O v -TiO 2 -Cu heterojunction with oxygen vacancy (O v ) stabilized Cu nanoparticles (NPs) as active sites can effectively adsorb and activate N 2 molecules. The close contact between BiOBr and Ov-TiO 2 elevates the quick transmission of photogenerated electrons at the interface and the enrichment on Cu NPs. This work not only provides an efficient photocatalyst for the N 2 reduction, but also supplies theoretical support for identifying the active sites and charge transfer kinetics of the nitrogen reduction reaction.

研究领域: 材料科学 · 环境科学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2022 · IF 24.319

Understanding the self-catalyzed decomplexation mechanism of Cu-EDTA in Ti3C2Tx MXene/peroxymonosulfate process

Daoyuan Zu,Haoran Song,Changping Li,Yuwei Wang,Rong Du,Rui Zhou,Wei Zhang,Shiting Pan,Yang Cai,Yongming Shen,Zhifeng Yang

Self-catalyzed decomplexation of Cu-ethylene diamine tetraacetic acid complex (Cu-EDTA) and recovery of Cu without addition of extraneous transition metals were achieved in Ti 3 C 2 T x MXene/peroxymonosulfate (Ti 3 C 2 T x /PMS) process. Free radical quenching experiments and electron spin resonance (ESR) measurements demonstrated that both hydroxyl radical (HO • ) and sulfate radical (SO 4 •- ) contributed to the degradation of Cu-EDTA. Activation of PMS by Ti 3 C 2 T x initiated Cu-EDTA decomplexation and released free Cu ions . Then, the formation of Ti-O-Cu bonds between Cu ions and Ti 3 C 2 T x accelerated the electron transfer from Ti 3 C 2 T x to Cu(Ⅱ) and triggered Cu(Ⅱ)/Cu(Ⅰ) cycle, which further enhanced PMS activation and led to the self-catalyzed decomplexation of Cu-EDTA. Simultaneous recovery of Cu was achieved due to the excellent absorption performance of negative charged Ti 3 C 2 T x towards Cu ions. This study revealed the self-catalyzed decomplexation mechanism of Cu-EDTA in the Ti 3 C 2 T x /PMS process and provided a feasible strategy for heavy metal complexes treatment.

研究领域: 环境科学 · 材料科学
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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

Effects of Fe(III) and Cu(II) on the sorption of s-triazine herbicides on clay minerals

Jun Wu,Wenzhong Zhang,Chunping Li,Erdan Hu

The effects of Fe(III) and Cu(II) on the sorption of atrazine (AT) and prometryn (PY) on clay minerals were investigated both preloaded and in solution. For smectite , Fe(III) preloading greatly enhanced AT and PY sorption at pH 4.0 and 6.0 but diminished AT sorption at pH 8.0. Cu(II) preloading promoted AT and PY sorption under alkaline conditions but suppressed AT sorption at pH 4.0. The adverse effects were not obvious for PY. While for illite and kaolinite , Fe(III) and Cu(II) had little or promotion effects due to the lower contents of them in these two minerals. In the co-sorption studies, for smectite, AT sorption remained at pH 4.0 and increased at pH 6.0 and 8.0, while PY sorption was inhabited over the pH range of 4.0–8.0 in the presence of Fe(III). AT and PY sorption were not affected by Cu(II) except for PY at pH 8.0, in which case, the sorption was promoted. For illite and kaolinite , Fe(III) and Cu(II) generally enhanced AT and PY sorption.

研究领域: 环境科学 · 土壤学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2022 · IF 6.76

Construction of the π-complexation desulfurization adsorbent containing Cu+ at defective sites of UiO-66

Yachun Ren,Yueyang Xu,Erjian Huang,Peng Zhang,Yongping Zeng

Adsorption desulfurization is a very effective method to remove thiophenic compounds from fuels. The metal–organic frameworks (MOFs) have emerged as a new type of desulfurization adsorbents because of their porous nature and large specific surface area. In this study, Cu 2+ was covalently introduced into the UiO-66 framework at the defective sites by the solvothermal method. Further, the π-complexation adsorbent UiO-66-Cu(I) containing Cu + for adsorption desulfurization was synthesized by the methanol vapor-induced reduction. The adsorption performance was tested for the removal of thiophene from the model fuels with different sulfur concentrations. In comparison with the pristine UiO-66, the adsorbent UiO-66-Cu(I) has a higher adsorption capacity for thiophene, reaching 14.8 mg S/g. The competitive adsorption results indicated that UiO-66-Cu(I) has good selectivity for thiophene in the presence of aromatic compounds. From the recycling experiments, this adsorption still has the 86 % of the initial capacity after four cycles, indicating that the adsorbent has a good recycling performance.

研究领域: 材料科学 · 环境科学
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PROCESS SAFETY AND ENVIRONMENTAL PROTECTION · 2023 · IF 7.8

Removal of As(Ⅲ) and As(Ⅴ) from mine groundwater using bimetallic Fe/Cu nanoparticles

Zibin Pan,Qingqiang Gao,Zuliang Chen

The elimination of arsenic (As) from arsenic-contaminated mine groundwater has become a worldwide problem because it causes environmental degradation and poses serious risks to human health. In this study, biosynthesized Fe/Cu nanoparticles (Fe/Cu NPs) were used for the simultaneous elimination of As(Ⅲ) and As(Ⅴ) from aqueous solution, resulting in their maximum amounts removed at 8.5 and 17.5 mg/g, respectively. SEM, FTIR, and XPS characterizations indicate that the Fe component on the Fe/Cu NPs acted as an adsorption and catalyst, while the Cu component mainly developed into a co-precipitation reaction with the As species, also facilitating the Fe catalytic processed. Meanwhile, adsorption isotherms , kinetics, and DFT calculations reveal that the removal of As(Ⅲ) was primarily physical/chemical adsorption and oxidation , while the elimination of As(Ⅴ) was co-precipitation and chemisorption. The most stable adsorption site, receiving 0.252 and 0.306 electrons from As(Ⅲ) and As(Ⅴ), respectively, was the unsaturated complexes of iron on the Fe/Cu NPs. Finally, the measurements and XPS results of Fe/Cu NPs in the treatment of groundwater show that the reduced capacity to remove As was attributed to a complex reaction system that disrupted the function of the Cu component, including co-precipitation and made the catalytic process possible. This explains there are differences in the reaction processes of biosynthetic Cu/Fe NPs in aqueous solution and groundwater.

研究领域: 环境科学 · 纳米技术 · 水处理
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JOURNAL OF ELECTRONIC MATERIALS · 2016 ·Vol. 46 ·期 5 ·2697-2704 · IF 1.491

Fabrication of Cu-Doped Bi2Te3 Nanoplates and Their Thermoelectric Properties

Liu Shuai,Peng Nan,Bai Yu,Ma Dayan,Ma Fei,Xu Kewei

Cu-doped Bi 2 Te 3 hexagonal nanoplates were fabricated by a simple solvothermal method. Scanning electron microscopy and transmission electron microscopy characterization illustrated that the nanoplates are single-crystal ones with an average width of 300 nm and thickness in the range of 20–30 nm. It was demonstrated that Cu x Bi 2 Te 3 nanoplates possess the lowest thermal conductivity (0.8–1.2 W/m K) at 300 K, which is mainly due to the enhanced phonon scattering by grain boundaries. Furthermore, the doped Cu could evidently enhance the power factor of Bi 2 Te 3 through optimizing the carrier transport properties. As a result, Cu 0.02 Bi 2 Te 3 nanoplates exhibit the best thermoelectric performance with a figure of merit of 0.33, which is more than two times higher than that of Bi 2 Te 3 nanoplates.

研究领域: 材料科学 · 热电材料研究
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Frontiers in Chemistry · 2021 · IF 5.221

Cu-Based Conductive MOF Grown in situ on Cu Foam as a Highly Selective and Stable Non-Enzymatic Glucose Sensor

Hu Qin,Qin Jie,Wang Xiao-Feng,Ran Guang-Ying,Wang Qiang,Liu Guang-Xiang,Ma Jian-Ping,Ge Jing-Yuan,Wang Hai-Ying

A non-enzymatic electrochemical sensor for glucose detection is executed by using a conductive metal–organic framework (MOF) Cu-MOF, which is built from the 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligand and copper acetate by hydrothermal reaction. The Cu-MOF demonstrates superior electrocatalytic activity for glucose oxidation under alkaline pH conditions. As an excellent non-enzymatic sensor, the Cu-MOF grown on Cu foam (Cu-MOF/CF) displays an ultra-low detection limit of 0.076 μM through a wide concentration range (0.001–0.95 mM) and a strong sensitivity of 30,030 mA μM−1 cm−2. Overall, the Cu-MOF/CF exhibits a low detection limit, high selectivity, excellent stability, fast response time, and good practical application feasibility for glucose detection and can promote the development of MOF materials in the field of electrochemical sensors.

研究领域: 材料科学 · 电化学传感器 · 生物医学工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2023 · IF 5.2

3D flower-like Cu-BiOCl/Bi2S3 heterostructure with synergistic Cu ion doping: A study on efficient tetracycline degradation under visible light

Yanjie Han,Zhijia Zhu,Chunyan Hu,Jian Zheng,Baojiang Liu,Wei Wang

In this study, a novel three-dimensional, flower-like Cu-BiOCl/Bi 2 S 3 photocatalyst was synthesized using a two-step calcination and hydrothermal method , aiming at the efficient removal of tetracycline (TC). Through comprehensive characterization techniques, it was discerned that the incorporation of Cu ions extended the light absorption range of BiOCl. Additionally, the formation of a heterojunction significantly enhanced the separation efficiency of space charge. The unique three-dimensional flower-like architecture of the Cu-BiOCl/Bi 2 S 3 photocatalyst augments its surface area exposure and consequently, the density of active sites. This catalyst exhibited a remarkable degradation rate of approximately 95% for TC under visible light irradiation. This performance exhibits a notable enhancement over the degradation rates of BiOCl and Bi 2 S 3 , which are approximately 39% and 53% respectively, surpassing them by factors of 2.39 and 1.78. Electron spin resonance (ESR) analysis coupled with free radical trapping experiments pinpointed superoxide radicals (•O 2 - ) and photogenerated holes (h + ) as the pivotal active species orchestrating the photocatalytic degradation. Concludingly, a possible TC degradation pathway was proposed based on the intermediates generated during the photocatalytic reaction as detected by Liquid Chromatograph Mass Spectrometer (LC-MS) and Three-Dimension Excitation Emission Matrix (3D EEM).

研究领域: 环境科学 · 材料科学
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Journal of Materials Chemistry C · 2018 ·Vol. 6 ·期 30 ·8105-8114 · IF 5.976

Cu MOF-based catalytic sensing for formaldehyde

Ping Gao,Xiang-Ying Sun,Bin Liu,Hui-Ting Lian,Xin-Qiang Liu,Jiang-Shan Shen

Developing a catalyst with a uniform and well-defined crystal structure is very important to establish a catalytic sensing system with high efficiency. In this work, Cu-BTC metal–organic frameworks (MOFs) without a crystalline CuO or Cu2O phase were successfully synthesized by using a low temperature synthesis method, and the as-prepared Cu-BTC MOFs were found to have outstanding catalytic activity towards the traditional oxidase substrate, o-phenylenediamine (OPD), to generate a colored and fluorescent product. The results of the kinetics analysis revealed that the catalytic behavior of Cu-BTC MOFs towards OPD could well follow the typical Michaelis–Menten equation, indicative of a strong affinity between Cu-BTC MOFs and OPD. On the basis of these findings, taken together the condensation reaction between the –CHO group of formaldehyde and the –NH2 group of OPD to form Schiff base compounds, a novel Cu-BTC MOF-based catalytic sensing system for detecting gaseous formaldehyde could be successfully established.

研究领域: 催化 · 材料科学 · 分析化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Spontaneous spatial-optimizing CO2 electroreduction to C2H4 over dynamically synergistic Cu-Bi pair

Mengchen Wu,Yang Yang,Jing Zhao,Rui Liu

In CO 2 electroreduction, mutative intermediates and the challenging C C coupling necessitate the spatial interplay between active sites and through dynamically optimizing configurations. Herein, we anchor ethylenediaminetetraacetic acid (EDTA)-bonded Cu x+ /Bi 3+ pair within UiO-66 for a spontaneous spatial-optimizing CO 2 -to-C 2 H 4 electroreduction. Ab initio molecular dynamic (AIMD) simulation visualizes that such metal pair adaptively interacts with intermediates. Density functional theory (DFT) elicits the componential synergy, in which an upshift d-band of Cu activates CO 2 being protonated into *COOH while Bi site stabilizes oxygenated dimers for deep hydrogenation. The dynamic feature of such pair affords large freedom for sorption and migration of various intermediates, which consequently bestows UiO-66-EDTA/CuBi a maximal FE C 2 H 4 of 47 % and a total current density over 100 mA cm −2 in the flow cell.

研究领域: 材料科学 · 催化化学 · 能源转化
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2024 · IF 20.2

Stable Cu+/Cu2+ species derived from in-situ growing Cu-S-V bonds in CuVxS electrocatalysts enables high efficiency CO2 electroreduction to methanol

Xuli Hu,Zhen Zhang,Zhenyao Li,Yushan Wu,Wei Wei,Yao Wang,Junchen Xu,Mingyue Ding

Regulating oxidation state of Cu-based chalcogenides catalysts during electrolysis is of great significance for efficient CO 2 electrochemical reduction reaction (CO 2 RR) to methanol, which still remains a dramatic challenge. Herein, we construct a heterogeneous Cu 3 VS 4 /CuS electrocatalyst (denoted as CuV x S), in which the in-situ growing Cu-S-V bonds avoid the accumulated electrons on oxidized Cu sites and inhibit the deep reduction of CuS to metallic Cu during electrolysis, maintaining stable and abundant reactive Cu + /Cu 2+ species to promote CO 2 RR performance to methanol. By this design, the CuV 0.1 S catalyst achieves an ultrahigh methanol selectivity of 79.8 %. In-situ FTIR measurement reveals that the synergistic effect of Cu + /Cu 2+ species and Cu-S-V bonding facilitates the *CO adsorption and the subsequent *CO hydrogenation process, which improve the generation of *CHO and *OCH 3 intermediates for enhanced methanol selectivity. This work provides a new insight into stabilizing high oxidation state of Cu-based electrocatalyst to maintain sufficient active sites for CO 2 RR.

研究领域: 电化学 · 催化材料科学
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