DALTON TRANSACTIONS
·
2020
·Vol. 50
·期 1
·197-207
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IF 4.174
Yan Zhao,Lei Li,Bo Ding,Xiu-Guang Wang,Zheng-Yu Liu,En-Cui Yang,Xiao-Jun Zhao
Decontamination of industrial wastewater containing toxic organic dye molecules and oxoanions is urgently desirable for environmental sustainability and human health. Water-stable porous metal–organic frameworks (MOFs) have emerged as highly efficient photocatalysts and/or adsorbents for water purification through controllable integration of the constitutive requirements. To reveal the inclusion anion effect of microporous MOFs on wastewater treatment, two isostructural MOFs incorporating positive charge and semiconductive characteristics, {[Cu(tpt)]·3H2O·0.5SO4}n (1) and {[Cu(tpt)]·2H2O·ClO4}n (2, tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine), have been synthesized and employed as dual-functional materials for both dye photodegradation and oxoanion removal. The two MOFs possess the same 3-fold interpenetrating cationic backbones but are encapsulated by highly disordered sulfate or perchlorate in the open channels. These included anions have significantly tuned the hydrophilicity of the channels, extended the visible-light absorption, optimized the bandgap and decreased the conduction band potential. Under the low-energy irradiation of a 30 W LED lamp, MOF 1 has selectively and efficiently degraded rhodamine B compared to 2 with accelerated kinetics, resulting from the stronger reduction ability and less migration resistance of the photogenerated electrons. Instead, MOF 2 can quickly capture harmful MnO4− and Cr2O72− by exchanging with the entrapped ClO4−, with maximum adsorption amounts of 557 and 168 mg g−1, respectively, under ambient conditions. The improved decolorization of the aqueous solution over 2 benefits essentially from the shape and charge memory effect and the smaller hydration energy of ClO4− than SO42−. These interesting observations highlight the importance of the included anions inside the porous MOF semiconductors on wastewater treatment.
研究领域:
环境科学
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材料科学
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化学工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
·
IF 9.7
Chenglong Bao,Fengyu Wu,Fan Wang,Longyu Qiu,Menggang Li,Depeng Zhao,Yongsheng Yu,Weiwei Yang
The development of efficient heterogeneous catalysts for copper-catalyzed azide-alkyne cycloaddition (CuAAC) is crucial for overcoming the limitations of homogeneous systems, such as poor recyclability and catalyst leaching. In this study, we report the synthesis of nanosized hollow Cu(I)/Cu(II)-metal-organic frameworks (Nano-hollow Cu(I)/Cu(II)-MOF). The paddlewheel Cu(II) sites persist as robust structural nodes, while partial reduction engenders catalytically active planar tetranuclear Cu(I) sites strategically embedded within the framework. This unique architecture endowed Nano-hollow Cu(I)/Cu(II)-MOF with remarkable catalytic activity, achieving a turnover frequency (TOF) of 456.9 h −1 over 10 min for the CuAAC reaction between phenylacetylene and benzyl azide with a TOF 1.66-fold higher than the nanosphere control, underscoring the hollow structure's advantages. Moreover, the catalyst also demonstrated exceptional recyclability, maintaining a nearly constant catalytic conversion rate over 6 cycles. Theoretical calculations unveiled a dual‑copper synergistic mechanism, wherein coordinated charge redistribution mediated by both copper sites significantly lowered the activation barrier. The alkyne dehydrogenation is identified as the rate-determining step with a theoretical overpotential of 0.82 eV, which was pivotal for enhancing reaction efficiency. Beyond conventional catalysis, the Nano-hollow Cu(I)/Cu(II)-MOF exhibited versatile applicability, including rapid fluorescent molecule synthesis with a rate constant (k Flu ) of 0.1 min −1 and efficient DNA-templated ligation reactions with an apparent rate constant (k obs ) of 0.21 s −1 .
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Journal of Materials Chemistry A
·
2026
·
IF 9.5
Qing Cheng,Yuqi Zhang,Yingying Cao,Long Liu,Yanqiang Zhang
The novel ionic liquid-H2O2 propellants are urgently to solve the intrinsic ignition problem for achieving the aerospace applications. We addressed this issue by tuning the d-band center to adjust the catalyst's adsorption strength for IL/H2O2 toward the optimal value, thus enhancing catalytic activities for the efficient decomposition of H2O2 to generate reactive oxygen species. Herein, the regulation of the d-band center of Cu(I) in Cu(I)-MOF catalyst by precise ligand engineering design was studied. Remarkably, The Cu-S3 coordination of Cu-SH' shifts its d-band center closer to the Fermi level, promoting the adsorption of [BMIM]N(CN)2 and H2O2. Cu-SH' enables efficient H2O2 activation and robust •OH and 1 O2 generation to trigger the rapid self-ignition of [BMIM]N(CN)2-H2O2 propellant. The resulted tid as low as 18.4 ms is nearly 34% lower than that of homogeneous catalyst [FcCH2N(CH3)3]2[Cu2I4]. This work provides fundamental insights into the design of efficient ligand-based combustion catalysts for the higher performance of rockets and spacecrafts.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2020
·
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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INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Chunpei Yu,Bonan Gu,Jiaxin Wang,Junhong Chen,Wenchao Zhang,Wei Shi,Gexing Yang,Xiaoting Lei,Junwu Zhu
The development of green primary explosives has become a “holy grail” of energetic materials research. Cu-based 5-nitrotetrazolate is considered one of the most promising candidates due to its excellent blasting power and environmentally benign nature. However, synthesizing Cu-based 5-nitrotetrazolate controllably and securely remains highly challenging. Herein, room-temperature anodization of metallic Cu and a Cu(I)–imidazole nanowire array on copper substrates in a sodium 5-nitrotetrazolate electrolyte leads to in situ electrosynthesis of Cu(I) 5-nitrotetrazolate (DBX-1, CuNT) and its analogue, Cu(II) 5-nitrotetrazolate [Cu(NT)2], respectively. Both obtained CuNT and Cu(NT)2 films demonstrate remarkable energy output and good laser-induced ignition performance. The thermal stability (Tp = 291 °C) and electrostatic safety (E50 = 2.54 mJ) of CuNT proved to be superior to those of Cu(NT)2 (Tp = 257 °C, and E50 = 0.57 mJ). Remarkably, this study provides an exciting new method for the rational design and development of Cu-based 5-nitrotetrazolate as a primary explosive for advanced initiating applications.
研究领域:
含能材料
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炸药化学
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电化学
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材料科学
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FOOD CHEMISTRY
·
2026
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IF 10.4
Mingzhu Liu,Xueyan He,Bo Peng,Jin Wu,Zunquan Zhao,Jialei Bai,Jingran Sun,Yanjun Fang
Highly mimetic enzymatic Mn₃O₄/gold nanoparticle (AuNP) composites were prepared, which catalyze the oxidation of tert-butylhydroquinone (TBHQ) to red 2-tert-butyl-1,4-benzoquinone (TBBQ) for TBHQ detection. Absorbance at 487 nm (A₄₈₇) correlates linearly with TBHQ concentrations in the range of 0.52–50 μg/mL, with a limit of detection (LOD) of 0.063 μg/mL, and a limit of quantification (LOQ) of 0.21 μg/mL. TBBQ quenches the fluorescence of copper/iodine-doped carbon dots (Cu,I-CDs) at 500 nm via the inner filter effect (IFE), forming an “on-off” fluorescence probe for TBHQ. TBHQ concentration correlates linearly with the fluorescence intensity difference (F₀ − F) in the range of 0.31–54 μg/mL, with an LOD of 0.054 μg/mL and an LOQ of 0.18 μg/mL. This study uses a dual-mode detection approach to determine TBHQ in various food samples, with recovery rates ranging from 82.5% to 103.0%. The method is sensitive, accurate, cost-effective, and suitable for the rapidly analyzing of TBHQ in food.
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Journal of CO2 Utilization
·
2018
·
IF 5.503
Xue-Dong Li,Yu Cao,Ran Ma,Liang-Nian He
Efficient CuI/1,10-phen-catalyzed three-component cascade reaction of propargylic alcohols, CO 2 , and 2-aminoethanols has been firstly developed for the thermodynamically favourable preparation of 2-oxazolidinones. In the presence of commercially available CuI, 1,10-phen (1,10-phenanthroline) and t -BuOK, the cascade reaction afforded the desired products in good to excellent yields with a broad substrate scope (14 examples). The predicted copper complex Cu 2 I 2 (phen) 2 in situ formed from CuI and 1,10-phen could activate the triple bond through coordination. The isolation of α-alkylidene cyclic carbonate as the reaction intermediate suggests that the carboxylative cyclization of propargylic alcohol with CO 2 , followed by ring-opening reaction, is involved in the one-pot three-component cascade reaction.
研究领域:
有机化学
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催化
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二氧化碳利用
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合成方法学
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JOURNAL OF HAZARDOUS MATERIALS
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2025
·
IF 11.3
Chao Xie,Pengyu Zhang,Yi Hu,Dandan Yang,Yahui Li,Yulian Li,Jiandong Lu,Zijian Wu,Junyong He,Peidong Hong,Lingtao Kong
Engineering a catalytic and hydrophilic membrane integrated system holds significant environmental implications for fouling-resistant and efficient water purification. The heterojunction Cu 2 O/Ti 3 C 2 T x was successfully synthesized by leveraging the specific interactions between the terminal active groups of MXene and Cu 2 O, effectively addressing the limitations of the catalytic membrane’s performance due to low-dose doping, and enhancing its catalytic activity and hydrophilicity. Here we report a ultra-low Cu(I) loading that achieves ultra-high fouling-resistance and decontamination performance in a self-cleaning Cu 2 O/Ti 3 C 2 T x @PVDF catalytic membrane integrated system. The representative membrane incorporating 1.0 wt% of Cu 2 O/Ti 3 C 2 T x (denoted as M-1.0) as a PMS activator demonstrated the successful performance of long-lasting antifouling and sustainable decontamination across a wide pH range in complex water matrices. The intrinsic Cu(I)/Cu(II) redox cycles was found to be crucial for driving PMS activation and oxidative conversion. Moreover, the Cu 2 O/Ti 3 C 2 T x -functionalized membrane demonstrated enhanced hydrophilicity and fouling-resistance compared to the pristine PVDF membrane. We further investigate the transformation and ecotoxicity of tetrabromobisphenol A and its intermediates within the M-1.0/PMS membrane system, providing valuable insights into the evolutionary dynamics of TBBPA. This work offers innovative perspectives for advancing environmental purification, membrane self-cleaning, and resources utilization technologies.
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CHEMOSPHERE
·
2023
·
IF 8.8
Huiwang Dai,Jingyi Zhu,Fanxu Meng,Daohui Lin,Wenjun Zhou,Dingjiang Chen,Ming Zhang,Qingqing Wang
In this study, Cu hybridization coupling oxygen defect engineering was adopted to synthesis of CuNiFe layered double oxides (CuNiFe-LDOs) in peroxymonosulfate (PMS) activation for degradation of methyl 4-hydroxybenzoate. The morphology and crystal structure of CuNiFe-LDOs was characterized in detail, which exhibited regular layered-structure at a Cu:Ni doping ratio of 1:1 and annealing temperature of 400 °C, and presented the crystal of Cu x O@Fe 3 O 4 –NiO. Besides, the X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) results demonstrated that abundant oxygen vacancies (OVs) and low oxidation state Cu species were composed in CuNiFe-LDOs400. The Cu 1·5 Ni 1·5 Fe 1 -LDOs400/PMS system showed excellent catalytic performance toward the degradation of butyl 4-hydroxybenzoate (BuP), and resistant to the effect of pH value and background inorganic anions. Based on quenching experiments and EPR measurements, singlet oxygen ( 1 O 2 ) was identified as the dominant active species during the heterogeneous catalytic process, which was generated by the synergistic interaction between OVs-Cu(I) site and PMS . In this process, the electron-drawing property of OVs promoted the adsorption of PMS molecule on Cu(I) site, followed by the accumulation of electron and cleavage of O–O bond to generate intermediate oxygen radical species, which donated one electron to eventually generate singlet oxygen.
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BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS
·
2024
·
IF 2.5
Hangyu Shen,Wenhui Liu,Yun Dou,Yongxin Lu,Chunling Zhang,Xiaoying Wang,Fangong Kong,Shoujuan Wang
In general, Cu(II) is the critical factor in catalyzing reactive oxygen species (ROS) production and accelerating amyloid-β (Aβ) oligomer formation in Alzheimer's disease (AD). Natural chelating agents with good biocompatibility and appropriate binding affinity with Cu(II) have emerged as potential candidates for AD therapy. Herein, we tested the capability of guluronic acid disaccharide (Di–GA), a natural chelating agent with the moderate association affinity to Cu(II), in inhibiting ROS production and Aβ oligomer formation. The results showed that Di−GA was capable of chelating with Cu(II) and reducing ROS production, even in solutions containing Fe(II), Zn(II), and Aβ. In addition, Di−GA can also capture Cu(II) from Cu−Aβ complexes and decrease Aβ oligomer formation. The cellular results confirmed that Di−GA prevented SH−SY5Y cells from ROS and Aβ oligomer damage by reducing the injury of ROS and Aβ oligomers on cell membrane and decreasing their intracellular damage on mitochondria. Notably, the slightly higher efficiency of Di–GA in chelating with Cu(I) than Cu(II) can be benefit for its in vivo applications, as Cu(I) is not only the most active but also the special intermediate specie during ROS production process. All of these results proved that Di–GA could be a promising marine drug candidate in reducing copper-related ROS damage and Aβ oligomer toxicity associated with AD.
研究领域:
神经科学
·
药理学
·
生物化学
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JOURNAL OF HAZARDOUS MATERIALS
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2020
·
IF 9.038
Junlei Zhang,Wei Zhao,Shanshan Wu,Renli Yin,Mingshan Zhu
Advanced oxidation processes (AOPs) based on heterogeneous catalytic activated peroxymonosulfate (PMS) have been becoming alternatives to conventional wastewater treatment technologies to directly degrade chemical contaminants. To build dual/multi redox cycles of different metal ions may be an effective means for better PMS activation. Herein, this study designed Mn 3 O 4 /CuBi 2 O 4 with dual redox cycles of Mn(III)/Mn(IV) and Cu(I)/Cu(II) to activate PMS for efficiently decomposing and mineralizing diclofenac sodium (DCF). Under optimal reaction conditions, DCF (50 mg/L) was degraded totally within 10 min, and TOC removal rate reached up to 74.3%. The possible mechanism of PMS activation by Mn 3 O 4 /CuBi 2 O 4 was proposed, wherein dual redox cycles of Mn(III)/Mn(IV) and Cu(I)/Cu(II) on Mn 3 O 4 /CuBi 2 O 4 effectively facilitated PMS activation to generate · O 2 − , 1 O 2 , SO 4 · − and · OH, which was responsible for DCF degradation. Moreover, combined with degraded products detected by high resolution liquid chromatography coupled to mass spectrometry and corresponding toxic assessment results, the possible degradation pathways of DCF were proposed and the relative toxicity of degraded products was evaluated. This work may be useful for developing stronger heterogeneous activators of PMS to construct more efficient AOPs for purifying wastewater.
研究领域:
环境科学
·
化学工程
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Shuohan Yang,Yonghou Xiao,Wuyue Zhang,Yu Qiao,Qidong Zhao,Ning Zhang,Gaohong He
Cuprous ion-based zeolites have been proven as promising carbon monoxide (CO) adsorbents by virtue of their excellent adsorption and regeneration properties due to π complexation. However, existing preparation methods still suffer from the problems of a cumbersome process and low loading amounts of cuprous ions. Herein, we proposed a one-step synthesis strategy of using ethanol as a solvent to provide a reducing protective environment, which enabled the facile and controllable preparation of highly dispersed CuCl over 5A zeolites. Using CuCl as a copper source, to ensure the integrity of the 5A zeolite structure, CuCl species were directly loaded onto the 5A support in one step. Ethanol solution could effectively protect Cu(I) from being oxidized by oxygen in air and improve the stability of cuprous ions in Cu(I)/5A adsorbents. The results demonstrated that the Cu(I)/5A prepared by this method exhibited a superior CO adsorption performance to the pristine 5A zeolite. The adsorption capacity of CO over Cu(I)/5A attained 3.44 mmol·g–1 at 298 K and atmospheric pressure, which was evidently superior to those of CuY (2.7 mmol·g–1) and CuSAPO34 (1.84 mmol·g–1) reported in the literature, while the adsorption capacity of H2 was only 0.069 mmol·g–1 under the same condition. According to the ideal solution adsorption theoretical model, CO was preferentially adsorbed and the IAST selectivity of CO in the CO/H2 binary mixture over Cu(I)/5A was about 273.4. This study provides a novel and effective way to synthesize high-efficiency CO adsorbents.
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