JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2019
·Vol. 166
·期 2
·D57
·
IF 3.12
Xinkuai He,Zhengyang Sun,Qingtian Zou,Luye Wu,Jianbing Jiang
The electrochemical behavior of Co(II) reduction and Co nucleation/growth process on glassy carbon (GC) electrode in 1-ethyl-3-methylimidazolium bisulfate ([EMIM]HSO4) ionic liquid (IL) and ethylene glycol (EG) system is investigated. Cyclic voltammetry (CV) measurements indicate that Co(II) reduction occurs by a one-step process, Co(II) to Co(0), and it is an irreversible reaction. The diffusion coefficient of Co(II) is 2.24 × 10−6 cm2 s−1 at 323 K in the system. Chronoamperometry measurements show that the growth/nucleation process of Co on GC electrode in [EMIM]HSO4-EG is a three-dimensional (3D) progressive nucleation at lower overpotentials and instantaneous nucleation at higher overpotentials under diffusion controlled growth process. These effects of electrodepositing potential, current density and temperature on Co coating thickness are also investigated. The Co coatings are observed by energy dispersive spectrometer (EDS), scanning electron microscope (SEM) and X-ray diffractometer (XRD). SEM micrographs confirm that the Co coatings are relatively loose with a fibrous surface morphology. XRD pattern of the prepared coating reveals the characteristic peak of crystalline Co with a preferred orientation direction and the average size of Co grains is 11 nm. The nanocrystalline Co coating exhibits an excellent catalytic activity and stability for hydrogen evolution reaction (HER) in alkaline medium.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Junren Zhu,Juanjuan Zou,Ting Peng,Xinyi Li,Chaohan Jiang,Shiyang Bai,Wei Ding,Zhenzhen Jiang
HCO 3 − coordination-enabled high-valent cobalt-oxo pathway absent without HCO 3 − • Quantitative Co(IV) contribution elevation from 2.5% to 28% with bicarbonate • Oxidation pathway switch from radical to non-radical regime by bicarbonate • CoCO 3 SO 3 2− complex identified as kinetically competent intermediate • Efficient performance across real waters with Co dosage below discharge limit Bicarbonate, a ubiquitous constituent of natural waters, is typically regarded as a radical scavenger in sulfate-radical-based advanced oxidation processes (SR-AOPs); however, its coordinative interaction with the catalytic metal center and the consequent modulation of oxidative pathways remain poorly understood. In this work, the role of HCO 3 − in the Co(II)-catalyzed activation of calcium sulfite (CaSO 3 ) was systematically investigated. HCO 3 − species is identified to coordinate with Co(II) to assemble a ternary Co(II) − HCO 3 − −S(IV) complex that facilitates the rate-limiting Co(II)-to-Co(III) oxidation, while the subsequent Co(III) − HCO 3 − complexation prevents Co(III) precipitation and sustains the catalytic cycle. Critically, this coordination is a prerequisite for Co(IV) generation: by depressing the Co(IV)/Co(II) redox potential, it unlocks the otherwise forbidden oxygen-atom transfer pathway, yielding a non-radical oxidant entirely absent without HCO 3 − . Together with 1 O 2 , this HCO 3 − -exclusive Co(IV) pathway operates in parallel with the SO 4 •− radical pathway, redirecting the dominant oxidation mechanism from a radical-driven regime toward a non-radical-driven regime, accompanied by a pronounced reduction in apparent activation energy (37.46 kJ mol −1 ). This system functions effectively across a wide pH, exhibits high tolerance to common anionic interferents, and achieves efficient performance across multiple authentic water matrices. In short, this work establishes HCO 3 − as a coordination-directed switch that sustains the catalytic cycle while uniquely gating access to the Co(IV) oxidation pathway, offering a ligand-engineering strategy for tuning reactive species speciation in S(IV)-based AOPs. The HCO 3 − enhanced- and altered- CaSO3 activation by Co(II). Download: Download high-res image (301KB) Download: Download full-size image
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Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Jie Wang,Chaowu Wang,Qibo Zhang
Recycling secondary resources that are rich in valuable metals can help reduce dependence on primary metal ores, foster sustainable industrial development, and enhance the resilience of the metal resource supply chain. This study presents a facile solvent extraction strategy for the efficient recovery of cobalt and nickel from spent choline chloride-ethylene glycol (ChCl-EG, Ethaline) deep eutectic solvent (DES) using bis(2,4,4-trimethylpentyl) phosphonic acid (Cyanex272) as the extractant. By integrating a water-modification approach with pH regulation, the viscosity of the Ethaline system is significantly reduced, while the coordination structures of Co(II) and Ni(II) ions are altered from [CoCl 4 ] 2 ⁻ and [Ni(EG) 3 ] 2+ to [CoCl 2 (H 2 O) 2 (EG) 2 ] 0 and [NiCl(H 2 O) 2 (EG) 2 ] + . This dual modification enables selective extraction with recovery efficiencies exceeding 99 % for both metals, achieving a separation coefficient ( β Co²⁺/Ni²⁺ ) of 9550. Mechanistic insights from density functional theory (DFT) calculations reveal that the preferential extraction of Co(II) stems from its more negative Gibbs free energy change (ΔG Co(II) = -0.21 kJ/mol vs. ΔG Ni(II) = -0.04 kJ/mol) during complexation with saponified Cyanex272. Furthermore, the regenerated Ethaline and Cyanex272 exhibit exceptional stability, maintaining > 95 % extraction efficiency over 10 cycles. This work advances solvent extraction technology by demonstrating a synergistic water-pH strategy for DES-based systems, offering a facile and scalable pathway for recycling metal-laden DES-based electrolytes in industrial applications.
研究领域:
环境科学
·
化学工程
·
材料科学
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高影响因子
Desalination and Water Treatment
·
2025
·
IF 1
Jingyi Chen,Chunyu Ji,Junsheng Liu,Jie Zhang
A series of new PMDA@CS/PVA composite membranes were fabricated by the crosslinking of pyromellitic dianhydride (PMDA) with chitosan (CS) and poly(vinyl alcohol) (PVA) in the presence of glutaraldehyde (GA) as a crosslinking agent. While, their adsorptions for Cu(II), Co(II), and Ni(II) in a single- and multiple mixed solutions were investigated. It was found that the incorporation of PMDA in the membranes can significantly enhance the adsorption capacity of membranes for these metals. The fitting of kinetic modeling s showed that the sorption manner of Cu(II), Co(II) and Ni(II) on the membranes obeyed the quasi-2nd kinetic modeling, indicating that it was dominated by chemisorption. The kinetic rate constants K 2 of membranes A-E for Cu(II), Co(II), and Ni(II) were in the region of 0.005–0.02, 0.026–0.082, and 0.002–0.053 [g/(h·mg)], respectively. The fitting of sorption isotherm modeling followed the Langmuir isotherm equation and the maximal Langmuir adsorption capacities for Cu(II), Co(II), and Ni(II) could reach 36.466, 32.119, and 30.916 mg/g, respectively. In addition, in the multi-component solutions, these membranes exhibited better selection for Cu(II) in Cu(II), Co(II), and Ni(II) mixed solutions. Moreover, it can be recycled five times when an EDTA was used as a de-sorbent. The exploration based on statistical physics principle confirmed that the adsorption of these membranes for Cu(II) is a mono-ion manner. These findings suggest that PMDA@CS/PVA composite membranes are promising sorbents for the removal of toxic metal ions from waste vehicle power batteries or metal-bearing wastewater.
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高影响因子
TRANSITION METAL CHEMISTRY
·
2015
·Vol. 40
·期 7
·769-777
·
IF 1.306
Wang Hu,Zhang Xiao-Yin,Bi Cai-Feng,Fan Yu-Hua,Meng Xiang-Min
Abstract Three complexes, Zn(C 40 H 36 N 4 O 8 )·3CH 3 OH ( 1 ), Ni(C 40 H 36 N 4 O 8 )·3CH 3 OH ( 2 ) and Co(C 40 H 36 N 4 O 8 )·3CH 3 OH ( 3 ), with a sexidentate (N 2 O 4 ) symmetric bis-Schiff base ligand (C 40 H 36 N 4 O 8 = 1,2-bis(2-methoxy-6-formylphenoxy)ethane- l -tryptophan) have been synthesized and characterized by physicochemical and spectroscopic methods. The X-ray crystal structures show that the metal atoms of three complexes are all six-coordinated by two nitrogens from C=N groups, two oxygens from ether groups and two carboxylic oxygens in the mono-ligand, forming a distorted octahedral geometry. The complexes were screened as photocatalysts for the degradation of methylene blue, rhodamine B and methyl violet. All three complexes proved to be good candidates for the photocatalytic degradation of methylene blue and complexes 2–3 are also good photocatalysts for the degradation of rhodamine B. The mechanism of these photocatalytic degradations is discussed. Graphical Abstract The main characterization and photocatalytic experiment of three complexes.
研究领域:
无机化学
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材料科学
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高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2022
·Vol. 32
·期 48
·2209743
·
IF 19.924
Yi-Xuan Li,Jing Li,Dunru Zhu,Ju-Zheng Wang,Guo-Fang Shu,Junji Li,Sheng-Li Zhang,Xue-Ji Zhang,Serge Cosnier,Hai-Bo Zeng,Dan Shan
High electrocatalytic activity with tunable luminescence is crucial for the development of electrochemiluminescence (ECL) luminophores. In this study, a porphyrin-based heterobimetallic 2D metal organic framework (MOF), [(ZnTCPP)Co 2 (MeIm)] (1), is successfully self-assembled from the zinc(II) tetrakis(4-carboxyphenyl)porphine (ZnTCPP) linker and cobalt(II) ions in the presence of 2-methylimidazole (MeIm) by a facile one-pot reaction in methanol at room temperature. On the basis of the experimental results and the theoretical calculations, the MOF 1 contains paddle–wheel [Co 2 (-CO 2 ) 4 ] secondary building units (SBUs) axially coordinated by a MeIm ligand, which is very beneficial to the electron transfer between the Co(II) ions and oxygen. Combining the photosensitizers ZnTCPP and the electroactive [Co 2 (-CO 2 ) 4 ] SBUs, the 2D MOF 1 possesses an excellent ECL performance, and can be used as a novel ECL probe for rapid nonamplified detection of the RdRp gene of SARS-CoV-2 with an extremely low limit of detection (≈30 aM).
研究领域:
材料科学
·
分析化学
·
病毒学
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PubMed
高影响因子
CRYSTENGCOMM
·
2022
·Vol. 24
·期 30
·5410-5420
·
IF 3.756
Ling-Mei Zhang,Chao Feng,Yu-Meng Yang,Huan-Huan Huang,Guo-Ning Zhang,Yu-Cheng Wang,Hong Zhao
One-pot solvothermal reactions of CoCl2·6H2O with the semi-rigid ligand 3-(pyridin-4-yl)-1H-pyrazole-5-carboxylic acid under different reaction temperatures and stoichiometry conditions gave rise to three new complexes: [Co(Hppza)2(H2O)2] (1), [Co(Hppza)2]n (2) and [Co(Hppza)(H2O)Cl]n (3), which were characterized by elemental analysis, FT-IR spectroscopy, UV-vis absorption spectroscopy, thermogravimetric analysis (TGA) and X-ray diffraction methods. A comparative study revealed the marked sensitivity of the structural chemistry of the above-mentioned ligand to the synthesis conditions. Complex 1, which exhibited a zero-dimensional (0D) structure of mononuclear cobalt(II), was formed at 120 °C with a metal-to-ligand molar ratio of 2 : 1. A further increase in the reaction temperature to 130 °C resulted in the two-dimensional (2D) structure of 2. Moreover, the three-dimensional (3D) structure of 3 was formed when the metal-to-ligand molar ratio was changed to 1 : 1 at 130 °C. The magnetic measurements of 3 showed weak ferromagnetic coupling with the decrease in temperature from 8 to 30 K and antiferromagnetic interaction among the CoII ions. In addition, the luminescence and electrogenerated chemiluminescence (ECL) behavior of 1–3 were also studied.
研究领域:
无机化学
·
材料科学
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高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2015
·
IF 2.133
Fei Yin,Jing Chen,Yongfeng Liang,Yang Zou,Jiang Yinzhi,Jingli Xie
Two coordination polymers [Co(dnbab) 2 (bimb)](H 2 O) 4 ( 1 ) and [Zn(dnbab) 2 (bimb)](H 2 O) 5 ( 2 ) (Hdnbab=4-[(3,5-dinitrobenzoyl)amino]benzoic acid, bimb=1,4- bis (1-imidazolyl) benzene) have been solvothermally synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Complexes 1 and 2 are isostructures and each displays an one-dimensional (1D) zigzag chain, which further forms a 3D supramolecular architecture with 1-D channels via inter-chain π–π interactions and hydrogen bonds . Moreover, the magnetic properties of 1 and fluorescent properties of 2 have been investigated.
研究领域:
化学
·
材料科学
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2022
·
IF 14.224
Siyuan Di,Jiahao Wang,Yixin Zhai,Pin Chen,Tao Ning,Chunxiang Shi,Hucheng Yang,Yue Bao,Qiang Gao,Shukui Zhu
A series of Co(II)-CeO 2 mixed metal oxides were synthesized by a facile hydrothermal-calcination procedure for activating peroxymonosulfate (PMS) and degrading toxic and difficult biodegradable organics. Co(II)-CeO 2 showed excellent degradation performance toward rhodamine B (RhB), toluidine blue, methylene blue and diclofenac. RhB is a refractory organic contaminant , and ecotoxicological evaluation unraveled its harmfulness to the biosphere. RhB was selected as the model pollutant to investigate catalytic mechanisms. Parameters affecting degradation performance were profoundly investigated, including Co:Ce feed ratio, initial pH, PMS dosage, catalyst dosage, RhB concentration, coexisting ions and reaction temperature. Reaction mechanisms were proposed based on density functional theory calculations and identifications of reactive oxygen species . Improvements have been achieved in seven aspects compared to previous studies, including 100% degradation ratio in both real water samples and each reuse of the catalyst, ultrafast degradation rate, cost-effectiveness of the catalyst, toxicity-attenuation provided by the developed degradation method, high degree of mineralization for the model pollutant, negligible leaching of active sites, and the enhancement of catalytic performance by utilizing trace leached cobalt, endowing the technique with broad applicability and prospect.
研究领域:
环境科学
·
化学工程
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PubMed
高影响因子
POLYHEDRON
·
2024
·
IF 2.4
Gao-Sheng Zhu,Yu-Meng Wei,Dan Wang,Xuan-Zu Guo,Long Li,Yan-Ying Zheng,Yi Jia,Bao-Yi Yu,Qiao-Xia Shang
Four new Zn(II)-, Cd(II)-, Mn(II)-, and Co(II) - based 1D to 2D coordination polymers (CPs) were synthesized from metal salts and 1,4-di(1-imidazol-1-yl)naphthalene (DIN) ligand via the coordination reaction under hydrothermal conditions with quantitative yields , namely, [Zn(SO 4 )(DIN)(H 2 O)] ( CP-1 ), [Cd(NO 3 ) 2 (DIN)] ( CP-2 ), [Mn(SO 4 )(DIN)(H 2 O) 3 ] ( CP-3 ), and [Co(NO 3 ) 2 (DIN) 2 (H 2 O) 4 ] ( CP-4 ). The CPs were analyzed and characterized using FT-IR, Elemental Analysis , TGA , SC-XRD, and PXRD . CP-1 was selected as a model sensor for fluorescence detection , and the sensor exhibited high quenching rates at two excitation wavelengths of λ ex = 230 and 290 nm, and at a single emission wavelength of λ em = 350 nm. At these two different excitation wavelengths, CP-1 behaved differently during the sensing of pesticides, and the highest quenching rate was achieved by the sensor for nitenpyram ( λ ex = 230 nm) and imidacloprid ( λ ex = 290 nm). Furthermore, during the sensing of vitamins, CP-1 encountered a strong quenching effect toward vitamin B2 . During the sensing processes, the inner filter effect (for nitenpyram , imidacloprid , and vitamin B2), fluorescence resonance energy transfer (for nitenpyram, imidacloprid, and vitamin B2), and photo-induced electron transfer (for vitamin B2) were the mechanisms responsible for fluorescence quenching .
研究领域:
化学
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材料科学
·
环境科学
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高影响因子
Separations
·
2024
·Vol. 11
·期 4
·116
·
IF 2.5
Guijiang Li,Wenze Xu
The escalating demand for cobalt in modern industry necessitates the recycling or extraction of this resource for sustainable development. Despite the abundance of lignin in nature, its utilization remains low, highlighting the need to enhance its value-added potential. This study focuses on the synthesis of quaternary ammonium lignin (QAL) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) as ionic liquid (QP–IL) compounds for the extraction of metal ions. A comparison of the extraction behavior of Co(II) and Ni(II) from chloride solution between QP–IL and P507 revealed varying extraction ratios under different conditions, with QP–IL demonstrating a higher cobalt extractability than P507. Furthermore, under identical conditions, QP–IL exhibited superior Co/Ni separation performance (βCo/Ni) compared to P507. Ultimately, QP–IL proved to be more effective than P507 in separating cobalt from mixed solutions.
研究领域:
化学工程
·
环境科学
·
材料科学
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高影响因子
JOURNAL OF INORGANIC BIOCHEMISTRY
·
2019
·
IF 3.224
Hu Wang,Cungang Xu,Xia Zhang,Dongmei Zhang,Fan Jin,Yuhua Fan
Six novel complexes, [Ni(C 36 H 34 N 2 O 10 )]·2.25CH 3 OH·0.5C 4 H 10 O ( 1 ), [Co(C 36 H 34 N 2 O 10 )] ( 2 ), [Cu(C 36 H 34 N 2 O 10 )]·2CH 3 OH ( 3 ), [Ni(C 36 H 32 N 2 O 8 Cl 2 )]·2CH 3 OH ( 4 ), [Co(C 36 H 32 N 2 O 8 Cl 2 )]·4CH 3 OH ( 5 ) and [Cu(C 36 H 32 N 2 O 8 Cl 2 )]·2CH 3 OH ( 6 ) with two sexidentate N 2 O 4 -donor bis-Schiff base ligands (C 36 H 34 N 2 O 10 = 1,2-bis(2-methoxy-6-formylphenoxy)ethane- l -tyrosine; C 36 H 32 N 2 O 8 Cl 2 = 1,2-bis(2-methoxy-6-formylphenoxy)ethane- l -4-chlorophenylalanine) have been synthesized and structurally characterized. Theoretical calculation of the six complexes was carried out by density functional theory (DFT) Becke's three-parameter hybrid (B3LYP) method employing the 6-3lG basis set, indicating that the calculation results are in accordance with experimental results. Moreover, the inhibitory activities of complexes 1 – 6 were tested in vitro against jack bean urease . At the same time, molecular docking was investigated to determine the probable binding mode. The experimental values and docking simulation exhibited that complexes 3 and 6 showed strong inhibitory activity (IC 50 = 10.36 ± 1.13, 15.63 ± 3.04 μM) compared with the positive reference acetohydroxamic acid (IC 50 = 26.99 ± 1.43 μM). Their structure-inhibitory activity relationship was further discussed from the perspective of molecular docking and theoretical calculation.
研究领域:
生物化学
·
计算化学
·
药物化学
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PubMed
高影响因子
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