JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2023
·Vol. 170
·期 10
·106506
·
IF 3.9
Yanli Wang,Rongfa Sun,Lingxu Yang,Huijun Liu,Chaoliu Zeng
In this paper, the electrochemical behavior of Zr(IV) and Y(III) in NaCl-KCl-K2ZrF6-YCl3 molten salts is studied by cyclic voltammetry, linear sweep voltammetry, and chronopotentiometry methods, which will provide a theoretical foundation for the preparation of Zr-Y alloy coating by molten salt electrodeposition method. Results show that the reduction of Zr(IV) on molybdenum electrode is a three-step charge-transfer process, while the reduction of Y(III) is a single-step diffusion-controlled three-electron quasi-reversible process at −0.30 V vs Pt. In addition, the diffusion coefficient of Y(III) in the melt at 750 °C is calculated as 2.15 × 10−5 cm2·s−1. The reduction of Zr(IV) and Y(III) on molybdenum electrode in NaCl-KCl-K2ZrF6-YCl3 molten salts has also been studied by cyclic voltammetry method. Results indicate that the Zr-Y alloy coating can be obtained on molybdenum electrode by galvanostatic electrolysis at −1.50 V vs Pt for 30 min.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2023
·
IF 6.6
Liyu Chen,Jiaxin Yang,Yifan Zhang,Shaohua Wu,Youjian Yang,Wenju Tao,Jiangyu Yu,Zhaowen Wang
The electrochemical behavior of Zr(IV) on a molybdenum (Mo) electrode in a KF-AlF 3 -Al 2 O 3 -ZrO 2 molten salt system was studied using cyclic voltammetry (CV), square-wave voltammetry (SWV) and chronopotentiometry (CP). The reduction process of Zr(IV) was found to follow a two-step, two-electron transfer mechanism: Zr(IV)+2e − →Zr(II) and Zr(II)+2e − →Zr(0). The reduction process was quasi-reversible and controlled by diffusion. Al-Zr alloys were successfully obtained on Mo and liquid aluminum electrodes by potentiostatic electrodeposition . Flower-like AlZr 3 and irregular granular Al 3 Zr were obtained on the Mo electrode, which were mainly attributed to the electrochemical co-reduction of Al(III) and Zr(IV) in the molten salt. Three Al-Zr alloy phases, Al 3 Zr , Al 3 Zr 2, and Al 2 Zr, were obtained on the liquid aluminum electrode, among which Al 3 Zr was dominant in the product, followed by Al 3 Zr 2 .
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2020
·Vol. 167
·期 2
·027519
·
IF 3.721
Jie Yuan,Li Jiang,Xiaopei Tan,Yuhua Yue,Haizhu Shi,Shun Feng
A facile way was developed to fabricate Zr(IV) cation modified gold electrode for high-performance electrochemical sensing of methyl parathion (MP) via layer-by-layer self-assembly. The electrode was prepared by sequentially absorbing 11-mercaptoundecyl-phosphoric acid (MDPA) and Zr(IV) cation on gold electrode through strong chelating interactions between gold and -SH as well as Zr(IV) cation and phosphoric groups of MDPA. Fourier transform infrared spectrophotometry, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and cyclic voltammetry were employed for the characterization of morphologies and electrochemical properties. The sensor was used to determine MP by square wave voltammetry. The cathodic peak current (at + 0.25 V vs saturated calomel electrode) increases linearly in the range of 1.0 − 180.0 ng ml−1 under optimized conditions. And the detection limit is low to 0.22 ng ml−1 (based on a signal-to-noise ratio of 3). The electrode is successfully used to detect MP in the real water sample with recoveries of 98.97%–102.4% and RSDs of 0.21%–1.99% (n = 3) at three spiked levels. The proposed method provides one simple way to prepare Zr(IV) cation modified electrode for the fast determination of MP. The reliability and accuracy of the method is validated by independent assays with HPLC.
研究领域:
分析化学
·
环境科学
✓ 已验证
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Zhaoyang Qi,Huaifang Li,Jie Chen,Changshen Ye,Ting Qiu
The carboxyl functionalized ionic liquid ([mim(CH 2 ) 3 COOH]Cl) was prepared as a linker to combine phosphotungstic acid (HPW) and Zr(IV) ion. The obtained [mim(CH 2 ) 3 COO] 3 PW-Zr composite acted as a heterogeneous catalyst for removing DBT from liquid fuel with H 2 O 2 as an oxidant. As a result, [mim(CH 2 ) 3 COO] 3 PW-Zr possessed high catalytic activity in extractive and catalytic oxidative desulfurization (ECODS). Moreover, the [mim(CH 2 ) 3 COO] 3 PW-Zr was further exploited to grow on the surface of PEI/silica gel. And the fabricated large-grained Zr-PWIL@PEI/silica gel was used in the continuous ECODS process, and the removal of DBT could still reach more than 95% after running continuously for 16 h. More importantly, the synergistic catalytic mechanism between HPW and Zr(IV) in the ECODS process has been investigated in detail by experiments and DFT calculations. As a result, a plausible mechanism has been proposed and verified, which contains two parts: the Lewis acidic center activating H 2 O 2 to form superoxide ion radicals ( OOH), and the OOH oxidizing HPW to peroxotungstate (W(O 2 ) n ), which has a high oxidizability and stability. Thus, the effective combination of Zr(IV) and HPW active sites is a very effective strategy to promote desulfurization efficiency and utilization efficiency of H 2 O 2 . Besides, we also found the distance between the corresponding active sites of catalysts plays an essential role in ECODS reaction as it strongly influences the synergistic effect between different active sites.
研究领域:
化学工程
·
催化科学
✓ 已验证
DOI
高影响因子
NUCLEAR TECHNOLOGY
·
2023
·
IF 1.5
Guanghui Wang,Hui He,Yaorui Li,Meng Zhang,Yang Gao,Caishan Jiao
The contaminated solvent from the Purex process is washed with alkaline detergents such as sodium carbonate, which generates a large amount of secondary wastes. Therefore, hydrazine carbonate as a salt-free reagent deserves to be studied in depth. In this study, the Ce(IV), U(VI), and Zr(IV) metal ions in organic phases containing dibutyl phosphate (HDBP) of 30% tributyl phosphate (TBP)–dodecane were washed with hydrazine carbonate. The effects of the oscillation time (1 to 15 min); temperature (25°C to 85°C); cumulative number of washes (one to four times); mass fraction of hydrazine carbonate (0.1% to 20%); volume ratio of the aqueous phase to the organic phase (0.2 to 5); HDBP concentration (0 to 0.4 M); HNO3 concentration (0.05 to 8 M); and concentration of Ce(IV), U(VI), and Zr(IV) metal ions on the removal percentages of Ce(IV), U(VI), and Zr(IV) metal ions in polluted solvents were studied. The results showed that when the organic phase containing 0.02 M HDBP was washed three times with 5% hydrazine carbonate at 25°C, the removal percentages of the Ce(IV), U(VI), and Zr(IV) ions were 96%, 98%, and 94%, respectively. Meanwhile, the retention concentrations of the three in the organic phase were 35, 28, and 78 mg/L, respectively. The increase of the mass fraction of hydrazine carbonate enhances the removal of the metal ions from the organic phase into the aqueous phase. High acid is not conducive to alkaline washing of metal ions. The increase of HDBP concentration not only promotes extraction but also increases the retention capacity of the organic phase and has the most significant effect on Zr(IV). U(VI) promotes the preferential washing of Zr(IV) while Ce(IV) increases the metal retention concentration of Zr(IV) in the organic phase.
研究领域:
化学工程
·
核化学与化工
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Shuangshuang Cen,Lijun Wang,Cong Wan,Xinyan Chai,Lei Li,Wensheng Linghu
Zr 4+ −O 2− pairs in MOFs and macromolecule − Zr(IV) complexes have proved one of the ideal catalytic components for catalytic transfer hydrogenation of biomass-derived furfural. However, restricted by limited adjustability of Zr 4+ −O 2− coordination environment and the complex design and creation of ligand defects, currently, there are only a few efficient low-temperature (<100 °C) catalytic systems. In this work, oxygenated groups enriched polyolefin − Zr(IV) complexes were prepared and fixed on/in mesoporous silica aerogel support. The complexes possessed a stable structure with C C bonds as the connecting skeleton of each oxygenated group, and the types and densities of oxygenated groups ( COOH, SO 3 H, and OH) could be easily adjusted by using different monomers. In the catalytic transfer hydrogenation reaction of furfural and 2-propanol, the catalyst synthesized using dicarboxylic maleic acid as a monomer of polyolefin exhibited the best catalytic performance in low temperatures, the main product furfuryl alcohol with a high yield of 96.0 % and a high selectivity of 98.2 % was obtained at 85 °C for 8 h. In 6 cycles of reactions at 85 °C, the furfuryl alcohol yield decreased gradually from 96 % in the 1st cycle to 84.0 % in the 4th cycle and further restored to 90.9 % and 89.3 % in the 5th and 6th cycles, respectively, by refreshing the used catalyst with methanol washing, and there was almost no leaching of Zr 4+ species in the reaction medium. The catalyst poisoning experiment with acidic and basic sites shielded by pyridine and boric acid, respectively, showed that the catalytic activity was more sensitive to the shielding of basic sites, and the isotope experiments revealed that two H of the product furfuryl alcohol are transferred from 2-propanol. Hereby, the oxygenated group-bearing polyolefin − Zr(IV) complexes with stable structure, variable functional groups and the corresponding various Zr 4+ −O 2– coordination pairs, are ideal catalyst candidates for the selective transfer hydrogenation of furfural to furfuryl alcohol.
研究领域:
催化化学
·
生物质转化
·
材料化学
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL RESEARCH
·
2021
·
IF 6.498
Junning Wang,Yujie Zhou,Minqian Zeng,Yanhong Zhao,Xiaoxin Zuo,Fanrong Meng,Fang Lv,Yu Lu
Recently, metal-organic frameworks (MOFs) have great potential as an emerging peroxide-mimicking enzyme, and the improvement of its enzyme-like activity is desired. There are few studies on improving the peroxidase-like activity of MOFs by using the strategy of size reduction. Moreover, it is challenging to enhance the activity of Zr-based MOFs with peroxidase-mimicking activity by size reduction strategy. In this work, the synthesis of Zr-based MOFs capped with polyvinylpyrrolidone (Zr-MOF-PVP) was firstly reported to reduce crystal size of peroxidase-mimicking enzyme for enhanced catalytic activity . Using the 3,3′,5,5′-Tetramethylbenzidine (TMB) as substrate, the synthesized Zr-MOF-PVP nanocomposites with nanosize (about 45 nm) possessed obviously enhanced peroxidase-like activity compared with the pristine Zr-MOF. Based on the above, the Zr-MOF-PVP was also successfully applied in constructing colorimetric detection. By using hydrogen peroxide (H 2 O 2 ) and phenol as the model analytes, the satisfactory detection performance was obtained, indicating that the proposed method had an attractive application prospect in the field of peroxidase-related detection. Besides, this work also provided a new perspective for improving the catalytic activity of nanozymes.
研究领域:
材料科学
·
纳米技术
·
分析化学
·
生物化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICAL SCIENCES
·
2024
·
IF 1.8
Liu Zhili,Yan Yumei,Li Jing,Zhou Wenfeng,Gao Haixiang,Lu Runhua
Heavy metal pollution has always been a great threat to human health and safety. Compared with other heavy metals, although zirconium ion (Zr(IV)) is equally harmful, due to the lack of research on Zr(IV) in the biological systems and environment, its detection does not seem to have received the attention it deserves. Herein, a rapid visual dual-mode detection (colorimetric and chrominance method) of Zr(IV) based on l -histidine functionalized gold nanoparticles (HIS-AuNPs) has been reported. AuNPs and HIS-AuNPs before and after adding Zr(IV) were characterized by UV–Vis, TEM, DLS, Zeta potential, EDS and FT-IR, etc. These results showed that l -histidine was successfully modified on the surface of AuNPs by forming a stable Au–N bond, and its modification had little effect on the dispersion degree of AuNPs. After the addition of Zr(IV), interaction of this metal ion with the imidazolyl group on l -histidine can obviously cause the aggregation of HIS-AuNPs within 12 min, and the dispersion state and particle size of HIS-AuNPs can be significantly changed. These two detection modes were established by means of absorbance and color change of solution, and being used in addition and recovery experiments of Zr(IV) in natural water. Under the optimal conditions, these two modes exhibited good linearity within 15–70 and 20–100 μmol L −1 , and limit of detection of 2.62 and 6.25 μmol L −1 . The proposed method was highly sensitive and selective, which provided a new convenient way to realize the detection of Zr(IV). Graphical abstract
研究领域:
环境科学
·
分析化学
·
纳米技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry B
·
2022
·Vol. 10
·期 44
·9258-9265
·
IF 7.571
Chenglong Dong,Mengfan Lu,Hailong Fan,Zhaoxia Jin
Developing advanced soft machines and tissue engineering for load-bearing cartilage or tendons requires tough hydrogels. However, the construction of double or triple crosslinked networks for these tough hydrogels, i.e., a strong network crosslinked by covalent bonds and one or two sacrificial networks built by hydrogen bonds or coordinate bonds, generally asks for multiple steps. It remains a challenge to develop hydrogels with a combination of excellent toughness and a high content of water through the time-saving one-pot process. This study demonstrates that this puzzle could be solved through engineering zirconium(IV)–amide coordinate bonds. To be specific, the combination of strong Zr(IV)–O and moderate Zr(IV)–N coordinate bonds in Zr-polyacrylamide (Zr-PAAm) hydrogels has the advantage that they are usually generated through multiple cross-linked networks. Compared to chemical crosslinked PAAm hydrogels, the highly transparent Zr-PAAm hydrogels crosslinked by Zr(NO3)4 displayed a 26-times increase in fracture stress, 4-times in fracture strain, 6-times in elastic modulus, and over 250-times in toughness. Besides, the mechanical properties of Zr-PAAm hydrogels could be altered over a wide range via changing the anion species, showing a dependence on the Hofmeister effect. The co-existence of Zr(IV)–N and Zr(IV)–O has been confirmed through XPS and FTIR characterizations. In particular, the effect of Zr(IV)–N in Zr–PAAm hydrogels has been verified by comparing the property changes of Zr-PAAm hydrogels before and after swelling in water, in which the Zr(IV)–N in the as-prepared hydrogels was replaced by Zr(IV)–O in the swollen gels. With ultra-stretchability and high transparency, the colorless Zr-PAAm hydrogels displayed rich interference colors under stretching, which brought great potential in anti-counterfeiting materials.
研究领域:
材料科学
·
生物医学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MICROCHEMICAL JOURNAL
·
2023
·
IF 4.8
Shiyi Chen,Feiyang Tian,Juan Peng,Yan Meng,Yu Wang,Xiaogang He,Qian Wang,Ganghui Chu
Chemical warfare agents, especially organophosphorus warfare agents are a variety of various chemical substances employed in warfare that can massively cause damage to the organism even death. The partial catalytic function of Universitetet i Oslo-66 (UiO-66, a zirconium-based metal–organic framework) produced via de novo synthesis is similar to calf intestinal alkaline phosphatase (CIAP, EC 3.1.3.1) and has a lower usage cost, is expected to be a mimetic enzyme for hydrolyzing organophosphorus warfare agents due to the fact that it has lattice defects. 0.1–5.6 mL of acetic acid was added as a regulator to form different lattice defects. Typically, mimetic enzyme activity tests often require expensive reagents as substrates, and the experiment processes are time-consuming and inconvenient. As a result, a novel approach based on near-infrared spectroscopy (NIRs) was developed in this research for predicting UiO-66 mimetic enzyme activity. p -Nitrophenyl phosphate disodium salt ( p NPP) was selected as a lower toxic organophosphorus warfare agent to conduct the subsequent simulant research. The absorbance of the mimetic enzyme catalytic system was evaluated using Ultraviolet–Visible (UV–Vis) spectroscopy to investigate the amount of its activity and compare it with CIAP activity. The synthesized samples’ enzyme activities ranged from 1.91 to 6.67 U/g and their catalytic costs ranged from 0.65 to 2.26 CNY. The powdered samples' near-infrared spectra were obtained. The sample’s enzyme activity data were linked with each sample’s original NIR spectra to establish the NIR model. A partial least squares (PLS) model of mimetic enzyme activity was developed by coupling spectral preprocessing with a variable screening technique. The root-mean-square error of cross-validation (RMSECV), the correlation coefficient of validation set (R) value, and the ratio of prediction to deviation (RPD) value were employed as assessment model indicators. The near-infrared spectrum model was developed by merging the best 2nd derivative spectral preprocessing with the Competitive Adaptive Reweighted Sampling (CARS) variable screening method. This model's RMSECV was 0.41 U/g, the correlation coefficient of calibration set (R_cv) value was 0.916, the root-mean-square error of prediction (RMSEP) set was 0.52 U/g, R was 0.948, and RPD was 2.51. As a result, the established model could be implemented to quantify the activity of UiO-66 quickly by including more variations of de novo -synthesized samples. The prediction method is simple, rapid, low cost and adaptable to be the theoretical and practical basis for further studying other interdisciplinary research work in biomimetic enzymology and spectroscopy.
研究领域:
化学
·
材料科学
·
酶学
·
光谱学
·
毒理学
✓ 已验证
产品关联
DOI
高影响因子
RADIOCHIMICA ACTA
·
2021
·Vol. 109
·期 10
·759-771
·
IF 1.44
You-qun Wang,Huan Wang,Yue Feng,Zhi-bin Zhang,Xiao-hong Cao,Yun-hai Liu
In this work, diethylenetriamine pentamethylenephosphonic acid (DTPMP) was ultilized into preparing of Zr(IV) organophosphates hybrids (Zr-DTPMP- x , x was the molar ratio of Zr(IV)/DTPMP in the synthetic process, x = 0.5, 1, 2, and 3) using a hydrothermal method. The physical and chemical properties of Zr-DTPMP- x were characterized by SEM&EDS, FT-IR, XRD, Zeta potential, XPS, TGA and contact angle analysis. Moreover, the adsorptive performances of Zr-DTPMP- x for U(VI) were investigated. The adsorption results showed that the optimum molar ratio of Zr(IV) to phosphine, pH, equilibrium time, and dosage was 0.5, 4.0, 180 min, and 10 mg, respectively. Besides, the adsorption of U(VI) was in accordance with the pseudo-second-order kinetic model and Sips isothermal model. Moreover, the adsorption capacity determined by Sips isothermal model was 181.34 mg g −1 for Zr-DTPMP-0.5. Furthermore, the adsorptive selectivity of Zr-DTPMP-0.5 for U(VI) was superior than the others. Zr-DTPMP-0.5 may be a powerful candidate for diminishing the contamination of U(VI).
研究领域:
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2022
·
IF 3.841
Wei Qin,Xue Han,Junwei Wang,Xie Wang,Jianli Zhang
To design some excellent extractants for the separation of Zr(Ⅳ) and Hf(Ⅳ), a novel set of polyamidoamine dendrimers peripherally modified with salicylaldehyde (Abbreviated as PAMAM-SA) have been synthesized. UV-vis absorption and fluorescent spectrometry were used to study the selectivity of G.1.0, G2.0, G3.0 and G4.0 PAMAM-SA on Zr(Ⅳ) and Hf(Ⅳ) compared with other metal ions, and their extraction/separation performance on Zr(Ⅳ) and Hf(Ⅳ) was also investigated under different pH solutions. The results show that these dendrimers have superior selectivity on Zr(Ⅳ) and Hf(Ⅳ) as compared with Ca 2+ , Mg 2+ , Fe 3+ and Ni 2+ ions. The binding stoichiometry of G1.0, G2.0, G3.0 and G4.0 PAMAM-SA dendrimers with Zr(Ⅳ) is 1:4, 1:8, 1:10, 1:16 molar ratio determined by fluorescent titration respectively and the molar ratio of these dendrimers with hafnium is similar to that of zirconium. Both of the maximum extraction efficiency (EE%) on Zr(Ⅳ) and the separation coefficient (β Zr/Hf ) are following the order of G2.0-PAMAM-SA > G1.0-PAMAM-SA > G3.0-PAMAM-SA > G4.0-PAMAM-SA, and the maximum EE% on Zr(Ⅳ) is up to 98.9% and furthermore the β Zr/Hf is 1.52 for G2.0-PAMAM-SA at lower acid concentration compared with the reported extractants. The favorable higher EE% and β Zr/Hf indicate that G2.0-PAMAM-SA may be potentially employed as a highly selective and efficient extractant to enhance separating zirconium from hafnium.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）