INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Yanhong Zhu,Zhongkui Li,Wenjing Song,Maroof Ahmad Khan,Hui Li
The conformation of the pentose ring in nucleotides is extremely important and a basic problem in biochemistry and pharmaceutical chemistry. In this study, we used a strategy to regulate the conformation of pentose rings of nucleotides via the synergistic effect of metal-ion coordination and π–π stacking. Seven types of coordination complexes were developed and characterized using Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, ultraviolet–visible spectroscopy, 1H nuclear magnetic resonance spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. On the basis of two conformational parameters obtained from single-crystal structure analysis, i.e., the pseudorotation phase angle and degree of puckering, the exact conformation of the furanose ring in these coordination polymers was unequivocally determined. Crystallographic studies demonstrate that a short bridging ligand (4,4′-bipyridine) is conducive to the formation of a twist form, and long auxiliary ligands [1,2-bis(4-pyridyl)ethene and 4,4′-azopyridine] induce the formation of an envelope conformation. However, the longest auxiliary ligands [1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene] cannot limit the flexibility of a nucleotide. Our results demonstrated that the proposed strategy is universal and controllable. Moreover, the chirality of these coordination polymers was examined by combining the explanation of their crystal structures with solid-state circular dichroism spectroscopy measurements.
研究领域:
生物化学
·
药物化学
·
晶体学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2022
·Vol. 169
·期 10
·106507
·
IF 4.386
Mengxue Huang,Ruimin Ding,Jie Yang,Wenwen Shi,Shufang Shi,Lifang Chen,Shanshan Liu,Xi Yin
Platinum group metal-free catalysts based on transition metal and nitrogen co-doped carbon materials are gaining attention for their applications in electrocatalysis. Nitrogen-coordinated metal sites (MNx) have been identified as the main active sites in PGM-free catalysts. Current synthetic approaches rely on the high-temperature treatment to introduce targeted electroactive MNx sites into the carbon matrix. In this study, we demonstrated the formation of MNx sites on Ni- and N-co-doped carbon templates via the solution-phase coordination with target metal ions, including Fe2+, Fe3+, and/ Co2+. The formation of MNx sites was confirmed via a combined approach of various physical characterization techniques, elemental analysis, and electrochemical analysis. The results indicate that the metal-vacancy-Nx sites in the template can coordinate with target ions to form electrochemically active MNx sites. By varying heat-treatment temperature, the amount of FeNx sites formed via coordination with Fe2+ ion can be tuned and correlated with the change of activity toward oxygen reduction reaction. The amount of MNx sites formed via solution-phase coordination with various ions followed the sequence of Co2+ > Fe2+ > Fe3+. These findings may further guide the future development of MNx-C electrocatalysts through this solution-phase coordination approach.
研究领域:
材料科学
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电化学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Fengliang Cao,Wanxin Ni,Qingshan Zhao,Libo Wang,Song Xue,Yanpeng Li,Debin Kong,Mingbo Wu,Linjie Zhi
Manipulating the local coordination environment holds immense potential in augmenting the catalytic performance of single-atom catalysts, which remains a great challenge. Through theoretical prediction, we find the catalytic properties of atomic Co centers towards selective hydrogenation of nitroarenes can be effectively manipulated by adjusting the coordinated number of P atoms, among which Co-N 2 P 2 configuration stands out. Accordingly, a single-atom Co 1 -N/P-C catalyst featuring Co-N 2 P 2 coordination was precisely fabricated through a sacrificial P-doped g-C 3 N 4 -template strategy. The optimal electronic structure of Co-N 2 P 2 enables favorable chemical affinities toward nitroarene and H 2 , promoted heterolytic dissociation of H 2 , and accelerated reaction kinetics. Consequently, the Co 1 -N/P-C catalyst exhibits outstanding catalytic activity (overall TOF of 241.5 h −1 ), selectivity (>99%), and exceptional stability towards the hydrogenation of various functionalized nitroarenes, far surpassing other coordination configurations and most reported non-precious metal catalysts. This work deepens our understanding of the relationship between coordination structure and catalytic performance, offering boosted single-atom catalysts for selective hydrogenation of nitroarenes.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2022
·
IF 10.508
Guoli Lu,Huayu Qiu,Xiaofan Du,Keval K. Sonigara,Jinzhi Wang,Yaojian Zhang,Zheng Chen,Lin Chen,Yongwen Ren,Zhiming Zhao,Junzhe Du,Suying Li,Jingwen Zhao,Guanglei Cui
Solid polymer electrolytes (SPEs) offer a viable path for overcoming the interfacial problems caused by side reactions and irregular deposition in rechargeable Zn (zinc)–metal batteries. However, this potential has been hampered by limited Zn2+ mobility in polymers; a central conundrum remains on how to solvate Zn2+ strongly enough to free it from anionic traps but weakly enough to minimize its migration barriers. Inspired by biologically dynamic Zn functions, we report a general strategy for constructing highly Zn2+-conductive SPEs by the engineering of heteroleptic coordination. Leveraging polymerization catalyzed by Lewis-acidic Zn2+ predissociated eutectics, we stoichiometrically integrate polymeric ligands (polyacrylamide) with kindred small-molecule co-ligands (acetamide) for Zn2+ centers. This heteroleptic configuration allows for the formation of entropy-increased ion channels with both labile Zn2+–polymer bonding and accelerated polymer mobility, warranting conductivity gains of 2 orders of magnitude and doubling the Zn2+-transference number to 0.44, compared with traditional SPEs. The applicability of the proposed heteroleptic coordination design is also demonstrated by the improved reversibility of Zn plating/stripping process (1200 h) and prolonged cycle life of solid Zn–metal batteries (350 cycles with Mo6S8 cathodes) with improved Coulombic efficiency (∼99%). This study underscores the importance of tailoring the coordination environment in improving cationic mobility in polymers.
研究领域:
材料科学
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电化学
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能源存储
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Lina Yan,Chao Wang,Yueshuai Wang,Yahui Wang,Zhaozhao Wang,Lirong Zheng,Yue Lu,Ruzhi Wang,Ge Chen
Electrochemical production of hydrogen peroxide (H 2 O 2 ) is a sustainable and environmentally benign process. The electrochemical oxygen reduction process (ORR) via a two electron pathway (2e - ORR) offers a practical method for on-site H 2 O 2 generation. As an earth-abundant catalyst, the cobalt-nitrogen coordinated systems integrated into the carbon matrix (Co-NC) has caused wide attention for its high activity in 2e - ORR. Even though most of the reported Co-NC catalysts have classical planar Co-N 4 coordination, axial coordination engineering has recently emerged as an effective way to control the active sites in the axial direction by using different coordination ligands. The structure-function link between the Co-N configuration of non-planar coordination and 2e - ORR activity is, however, not fully understood. An axial-N coordinated Co-N 5 motif embedded in hierarchically porous graphite-3R carbon (Co-N 5 C) was effectively synthesized using a template-sacrificing method. The Co-N 5 C has a high selectivity for 2e - ORR and a high H 2 O 2 molar production rate of up to 6.78 mol peroxide/g catalyst /h in acidic media, both of which are better than its Co-N 4 counterpart. DFT analyses demonstrate that axial-N ligands regulated the d -band center of the Co atom in the Co-N 5 C catalyst, inducing a shift in Δ G *OOH near the Sabatier volcano plot's peak (Δ G *OOH = 4.22 eV). This optimized the binding of the *OOH intermediate and then enhanced the protonation of *OOH to produce H 2 O 2 more efficiently.
研究领域:
材料科学
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电化学
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催化科学
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产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2025
·
IF 3.4
Hongyu Wang,Fumin Wang,Kaiwei Wang,Xubin Zhang,Changhao Bing,Xiaolu Fan,Tongxue Zhang,Syed Mujtaba ul Hassan
Developing an approach for the efficient synthesis of TS-1 zeolites with desirable morphologies and tunable coordination environments for Ti active sites is a pivotal challenge in the design of high-performance catalysts and zeolite crystal engineering. Herein, we report a cost-effective and efficient additive, guanidinoacetic acid (GAA), and conduct a systematic study on the synthesis of plate-like TS-1 zeolites using GAA as an additive. Introducing GAA during hydrothermal synthesis not only modulates the morphology of TS-1 crystals but also permits GAA to adequately chemically interact with titanium precursors to form hexa-coordinated Ti species. TS-1 zeolites with a controllable b-axis thickness in the range of 80–110 nm, and abundant framework Ti and hexa-coordinated Ti species are successfully achieved by optimizing the synthetic parameters. Through SEM, FT-IR, XPS, TEM, and XRD analysis, the mechanism of GAA altering crystal growth is mainly to inhibit the growth of the (010) plane. A b-axis-oriented TS-1 zeolite enriched with hexa-coordinated Ti species displays better catalytic performance in the 1-hexene epoxidation reaction than the conventional TS-1 zeolite containing only framework Ti species (35 vs 24%). This can be ascribed to the more active hexa-coordinated Ti species and shorter diffusion distance. This synthetic strategy provides a way to change the zeolite morphology and tune the number and distribution of Ti species in TS-1 zeolites.
研究领域:
催化材料
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晶体工程
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化学合成
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产品关联
DOI
高影响因子
Journal of Materials Research and Technology-JMR&T
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2023
·
IF 6.4
Zhenzhen Feng,Xiaomeng She,Jian Peng,Yujie Qiang,Song Zhang
Although magnesium alloys have been effectively used in industry, they have weak corrosion resistance. Herein, robust Ni-thiolate coordination polymer Mg(OH) 2 coatings were prepared by an oxidation-hydrolysis-coordination (OHC) strategy to make AZ31 magnesium alloy highly resistant to corrosion in 3.5 wt% NaCl solution. The OHC process includes three steps: I) oxidation of AZ31 to produce AZ31@MgO; II) hydrolysis of MgO to produce Mg(OH) 2 , cation exchange between Mg(OH) 2 and Ni(II) to produce Mg–Ni LDH; III) coordination of Ni(OH) 2 from Mg–Ni LDH by the 1,4-Benzenedithiol (BDT) ligand to produce LDH-BDT coatings. Potentiodynamic polarization, EIS, and in situ SRET in 3.5 wt% NaCl solution were used to assess the hybrid coating's anti-corrosion performance. Surprisingly, LDH-BDT coating achieves excellent corrosion inhibition performance (99.9999%) with the i corr of 1.926 × 10 −10 A cm −2 , which is six orders of magnitude lower than that of AZ31 substrate, this is due to the cooperative effect, such as the physical protection provided by thick LDH-BDT coatings and the hydrophobic properties of Ni(II)-BDT coordination polymers. This study provides fresh insight into the fabrication of Mg(OH) 2 -based coatings modified with Ni-thiolate complex to significantly improve Mg alloys' resistance to corrosion.
研究领域:
材料科学
·
腐蚀与防护
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2022
·
IF 7.968
Ling Hu,Zhiwen Wang,Yingzhang Shi,Cheng Liu,Yidong Hou,Jinhong Bi,Ling Wu
The defect-rich ultrathin WO 3 nanosheets are successfully prepared as photocatalysts via heating treatment for the pristine WO 3 nanosheets (NS) in vacuum (NSV) and N 2 atmosphere (NSN). The increment of degradation efficiencies of levofloxacin (LVX) over NS (49.9 %)
研究领域:
环境科学
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材料科学
·
化学
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产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Rongwei Xu,Guangxu Yao,Shicheng Xu,Danhong Li,Huijuan Zhang,Yu Wang
The rational design of single-atom catalysts (SACs) with tailored coordination environments is essential for improving their electrocatalytic efficacy. This study employs a coordination engineering approach to immobilize atomically dispersed nickel atoms on nitrogen-doped carbon nanofibers (NCNFs), forming a novel Ni–N2O2/NCNFs catalyst. Unlike the traditional Ni–N4 coordination configuration, each nickel atom in this Ni–N2O2 framework is stabilized within a rare and well-defined N2O2 coordination environment. This distinctive local structure is conclusively characterized using single-crystal X-ray diffraction and X-ray absorption spectroscopy. Consequently, the Ni–N2O2/NCNFs catalyst exhibits remarkable hydrogen evolution reaction activity in a 1.0 M KOH solution, necessitating an overpotential of merely 37 mV to attain a current density of 10 mA cm–2. These results confirm the broad-scale applicability of the strategy for modulating the local coordination chemistry of SACs and provide novel insights that will facilitate the design of highly efficient and stable catalysts for alkaline water splitting.
研究领域:
材料科学
·
电化学
·
催化
·
纳米技术
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产品关联
DOI
PubMed
高影响因子
Polymers
·
2020
·Vol. 12
·期 2
·442
·
IF 3.426
Guangtao Qian,Mengjie Hu,Shangying Zhang,Mengxia Wang,Chunhai Chen,Jianan Yao
To achieve polyimide-metal complexes with enhanced properties, 5-amine-2-(5-aminopyridin-2-yl)-1-methyl-benzimidazole (PyMePABZ) that contains stiff 2-(2′-pyridyl)benzimidazole (PyBI) was synthesized and exploited to construct the Cu(ΙΙ)-crosslinked polyimides (Cu-PIs). These Cu-PIs exhibited higher dielectric, thermal, and mechanical properties with an increase in Cu2+content. Among them, their dielectric constants (εrS) were up to 43% superior to that of the neat PI, glass transition temperatures (Tgs) were all over 400 °C, and 5% weight loss temperature (T5%) maintained beyond 500 °C. These data indicate that the metal coordination crosslinking provided a useful guide to develop high performance PIs which possess potential application as useful high temperature capacitors.Keywords:polyimide;metal coordination crosslinking;high performance
研究领域:
材料科学
·
化学工程
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DOI
PubMed
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 3
·904
·
IF 4.927
Gai Zhang,Yufan Zhang,Amin Tan,Yan Yang,Min Tian
Oxidative desulfurization (ODS) is the promising new method for super deep desulfurization of fuel oil. The oxidative desulfurization performance of the metal-N4-chelates metallophthalocyanines (MPcs) is related to the chemical properties of conjugate structures and the central metal ions. Herein, a biomimetic catalytic system composed of metallophthalocyanines (MPcR4, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); R = -H, -COOH, -NO2, -NH2) and molecular O2was performed to study the influence of MN4-type coordination structure in metallophthalocyanines for the degradation of dibenzothiophene (DBT) in model oil containing n-octane. The results reveal that the conjugate structures and the center metal ions of metallophthalocyanines played key roles in oxidative desulfurization performance. The inductive effect of different R substituents strongly affected the electron cloud distribution of the conjugate structures and the catalytic performance. Moreover, the catalytic activity of MPcs, which is related to the d electronic configuration and ligand-field effects, does not sequentially increase with the increase in the d electron number of central metal ions.Keywords:metallophthalocyanine;MN4-type coordination structure;desulfurization;O2
研究领域:
化学
·
环境科学
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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Wu Jine,Liao Chenyi,Li Tianyu,Zhou Jing,Zhang Linjuan,Wang Jian-Qiang,Li Guohui,Li Xianfeng
Membranes with fast and selective ion transport are essential for separations and electrochemical energy conversion and storage devices. Metal-coordinated polymers are promising for fabricating ion-conducting membranes with molecular channels, however, the structures and ion transport channels remain poorly understood. Here, we reported mechanistic insights into the structures of metal-ion coordinated polybenzimidazole membranes and the preferential K + transport. Molecular dynamics simulations suggested that coordination between metal ions and polybenzimidazole expanded the free volume, forming subnanometre molecular channels. The combined physical confinement in nanosized channels and electrostatic interactions of membranes resulted in a high K + transference number up to 0.9 even in concentrated salt and alkaline solutions. The zinc-coordinated polybenzimidazole membrane enabled fast transport of charge carriers as well as suppressed water migration in an alkaline zinc-iron flow battery, enabling the battery to operate stably for over 340 hours. This study provided an alternative strategy to regulate the ion transport properties of polymer membranes by tuning polymer chain architectures via metal ion coordination.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）