COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2022
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IF 5.518
Senyang Song,Xiaoyan Ma,Wenyue Li,Boyuan Zhang,Jing Sun,Chuyan Deng
In order to overcome the low capacitive performance of traditional metal organic frameworks (MOFs) applied to supercapacitors , a novel conjugated small molecule monomer(3,5-diaminobenzoic acid, DABA) with amino and carboxyl groups was used as a ligand, and Ni and Co ions as metal nodes to construct novel highly electroactive bimetallic MOF(DABA-MOF) materials through a simple one-step solvothermal method . The structure and capacitive performance of obtained DABA-MOF in three organic solvents with different polarities and degrees of deprotonation (methanol, ethanol, N,N-dimethylformamide) was investigated, and it was found that with the increase of solvent deprotonation degree, the morphology of DABA-MOF with the coexistence of amino and carboxyl groups gradually changes from a smooth rod-shaped solid structure to a rough hydrangea-like structure, and the corresponding capacitive performance of DABA-MOF is also gradually enhanced. In particular, DABA-MOF synthesized in DMF can reach a maximum specific capacitance of 621 C g −1 at 1 A g −1 , and the capacitance remains as high as 81.05% even after 5000 cycles, which exhibit excellent capacitance properties. This study shows that it has potential advantages to select the mixed coordination active MOF with amino and carboxyl groups as the electrode material for supercapacitor, and the deprotonation degree of solvent has a great influence on the structure and morphology of MOF with mixed active coordination sites.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED MATERIALS
·
2024
·
IF 27.4
Yafei Ding,Qingqing Cheng,Jing Lyu,Zengwei Liu,Ruizhe Yuan,Fengguo Ma,Xuetong Zhang
Microfluidic deprotonation approach is proposed to realize continuous, scalable, efficient, and uniform production of aramid nanofibers (ANFs) by virtue of large specific surface area, high mixing efficiency, strong heat transfer capacity, narrow residence time distribution, mild laminar-flow process, and amplification-free effect of the microchannel reactor. By means of monitoring capabilities endowed by the high transparency of the microchannel, the kinetic exfoliation process of original aramid particles is in situ observed and the corresponding exfoliation mechanism is established quantificationally. The deprotonated time can be reduced from the traditional several days to 7 min for the final colloidal dispersion due to the synergistic effect between enhanced local shearing/mixing and the rotational motion of aramid particles in microchannel revealed by numerical simulations. Furthermore, the cascade microfluidic processing approach is used to make various ANF colloidal aerogels including aerogel fibers, aerogel films, and 3D-printed aerogel articles. Comprehensive characterizations show that these cascade-microfluidic-processed colloidal aerogels have identical features as those prepared in batch-style mode, revealing the versatile use value of these ANFs. This work achieves significant progress toward continuous and efficient production of ANFs, bringing about appreciable prospects for the practical application of ANF-based materials and providing inspiration for exfoliating any other nano-building blocks.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Yu Wang,Yi Lu,Yiwei Shi,Jingjing Wang,Yingying Zheng,Jiaqi Pan,Chaorong Li,Jun Cao
Urea oxidation reaction (UOR) has been endorsed as an energy-saving approach for assisting hydrogen evolution, and Ni(OH) 2 -based catalysts has been widely used as efficient candidates for catalyzing UOR. However, the sluggish deprotonation process characterized by high energy barriers restricts the achievement of high efficiency. In this study, isoelectronic Co was introduced into Ni(OH) 2 by one-step hydrothermal reaction. The doped Co induced electrons located on Ni centre, and decreased the redox potential of Ni 2+ /Ni 3+ . Consequently, the performance of Ni(OH) 2 toward UOR was boosted, with the optimized 5 %Co-Ni(OH) 2 exhibiting the lowest potential of 1.357 V vs RHE at 100 mA cm −2 and outstanding stability operating over 100 h at 10 mA cm −2 . Moreover, a cell assembled by 5 %Co-Ni(OH) 2 /NF and Pt/C/NF outperformed better performance of urea electrolysis comparing with the commercial cell assembled by Pt/C/NF and RuO 2 /NF. Density functional theory (DFT) calculations revealed that the introduced Co regulated the electronic structure of Ni(OH) 2 , resulting in an optimized d-band centre. Moreover, the doped Co altered the initial adsorption coordination of urea molecules on NiOOH surface and reduced energy barrier for the consecutive deprotonation process (rate-determination step), which enhanced catalytic dynamic and subsequently led to a boosted performance toward UOR.
研究领域:
材料科学
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电化学
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理论计算
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
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2025
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IF 13.1
Chenyang Xia,Bowen Lu,Qi Xu,Nanxin Shen,Qiancheng Liao,Jiyun Cui,Baiyang Wang,Yueyang Sun,Changjiang Dong,Fei Gan
The discovery and engineering of prenyl diphosphate C-methyltransferases have facilitated the understanding and expansion of terpenoid diversity. Here, we report the structural and mechanistic characterization of a methyltransferase variant HumMT W197G that produces unconventional C11 prenyl diphosphates through an unusual dual deprotonation mechanism. Through protein engineering, we expanded the substrate-binding pocket of Micromonospora humi methyltransferase (HumMT) by W197G substitution, converting the substrate specificity from DMAPP and IPP (C5) to GPP (C10). Notably, HumMT W197G exhibits both C4 and C2 deprotonation, producing both iso-2-methyl-GPP and 2-methyl-GPP. Using cryogenic electron microscopy (cryo-EM), we solved the structures of apo-HumMT W197G, HumMT W197G-SFG, and HumMT W197G-SFG-Mg2+-GPP complexes to resolutions of 3.14, 2.97, and 2.3 Å, respectively. Through structure-guided engineering, molecular docking, and molecular dynamics simulations, we identified E168 as a catalytic base facilitating deprotonation at both the C2 and C4 positions. Additionally, we discovered W197Y as a critical mutation that discriminates between IPP and DMAPP substrates, leading to the identification of a natural methyltransferase from Micromonospora echinospora that produces noncanonical C7 prenyl diphosphates 2,2-dimethyl-IPP and 2,4-dimethyl-DMAPP. Our findings expand the understanding of methyltransferase catalytic mechanisms and demonstrate successful structure-based protein engineering to modulate carbocation intermediate deprotonation, providing implications for expanding terpenoid diversity.
研究领域:
生物化学
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结构生物学
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合成生物学
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酶工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Dandan Zhou,Youxi Wang,Yuniu Sun,Jiefu Zhang,Dan Wang,Zhenyu Li,Xiang Shao
The details of catechol interacting with the ZnO surfaces are critical for understanding how the organic chromophores anchor on and hence functionalize the ZnO materials. In this work, we apply low-temperature scanning tunneling microscopy (LT-STM) in combination with density functional theory (DFT) calculations to investigate the adsorption state and interface charge transfer of catechol on a ZnO(10-10) surface. For the molecules deposited at liquid nitrogen temperature, the fully-protonated (FP) status prevails in the isolated molecules despite the synergistic formation of half-protonated (HP) and fully-deprotonated (FD) ones. However, annealing to elevated temperature drives all the molecules to assemble into either linear or a c(2 × 2) superstructure composed of only FD catechols. Such spontaneous deprotonation of catechol is different from the predicted water-assisted process and plays critical roles in switching the catechol from electron acceptors to electron donors relative to the ZnO surface. These results may bring new insights into the design of optoelectronic and biomedical applications of the ZnO-organic compositional system.
研究领域:
材料科学
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表面化学
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产品关联
DOI
高影响因子
Journal of the American Chemical Society
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2015
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IF 12.113
Xiao-Li Pei,Yang Yang,Zhen Lei,Shan-Shan Chang,Zong-Jie Guan,Xian-Kai Wan,Ting-Bin Wen,Quan-Ming Wang
The activation of C(sp3)–H bonds is challenging, due to their high bond dissociation energy, low proton acidity, and highly nonpolar character. Herein we report a unique gold(I)–silver(I) oxo cluster protected by hemilabile phosphine ligands [OAu3Ag3(PPhpy2)3](BF4)4 (1), which can activate C(sp3)–H bonds under mild conditions for a broad scope of methyl ketones (RCOCH3, R = methyl, phenyl, 2-methylphenyl, 2-aminophenyl, 2-hydroxylphenyl, 2-pyridyl, 2-thiazolyl, tert-butyl, ethyl, isopropyl). Activation happens via triple deprotonation of the methyl group, leading to formation of heterometallic Au(I)–Ag(I) clusters with formula RCOCAu4Ag4(PPhpy2)4(BF4)5 (PPhpy2 = bis(2-pyridyl)phenylphosphine). Cluster 1 can be generated in situ via the reaction of [OAu3Ag(PPhpy2)3](BF4)2 with 2 equiv of AgBF4. The oxo ion and the metal centers are found to be essential in the cleavage of sp3 C–H bonds of methyl ketones. Interestingly, cluster 1 selectively activates the C–H bonds in −CH3 rather than the N–H bonds in −NH2 or the O–H bond in −OH which is traditionally thought to be more reactive than C–H bonds. Control experiments with butanone, 3-methylbutanone, and cyclopentanone as substrates show that the auration of the C–H bond of the terminal methyl group is preferred over secondary or tertiary sp3 C–H bonds; in other words, the C–H bond activation is influenced by steric effect. This work highlights the powerful reactivity of metal clusters toward C–H activation and sheds new light on gold(I)-mediated catalysis.
研究领域:
无机化学
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有机金属化学
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催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Linchen Xie,Anqi He,Da Li,Tianyi Li,Limin Yang,Kun Huang,Yizhuang Xu,Guozhong Zhao,Jingyu Liu,Kexin Liu,Jia’er Chen,Yukihiro Ozaki,Isao Noda
Single-crystal structures of myo-inositol complexes with erbium ([Er2(C6H11O6)2(H2O)5Cl2]Cl2(H2O)4, denoted ErI hereafter) and strontium (Sr(C6H12O6)2(H2O)2Cl2, denoted SrI hereafter) are described. In ErI, deprotonation occurs on an OH of myo-inositol, although the complex is synthesized in an acidic solution, and the pKa values of all of the OHs in myo-inositol are larger than 12. The deprotonated OH is involved in a μ2-bridge. The polarization from two Er3+ ions activates the chemically relatively inert OH and promotes deprotonation. In the stable conformation of myo-inositol, there are five equatorial OHs and one axial OH. The deprotonation occurs on the only axial OH, suggesting that the deprotonation possesses characteristics of regioselectivity/chiral selectivity. Two Er3+ ions in the μ2-bridge are stabilized by five-membered rings formed by chelating Er3+ with an O–C–C–O moiety. As revealed by the X-ray crystallography study, the absolute values of the O–C–C–O torsion angles decrease from ∼60 to ∼45° upon chelating. Since the O–C–C–O moiety is within a six-membered ring, the variation of the torsion angle may exert distortion of the chair conformation. Quantum chemistry calculation results indicate that an axial OH flanked by two equatorial OHs (double ax–eq motif) is favorable for the formation of a μ2-bridge, accounting for the selectivity. The double ax–eq motif may be used in a rational design of high-performance catalysts where deprotonation with high regioselectivity/chiral selectivity is carried out.
研究领域:
无机化学
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物理化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
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2023
·
IF 7.3
Jin Yuan,Zhiwei He,Hongbo Zhang
Selective C–H bond oxidation of cyclohexane into KA oil (ketone-alcohol) is of vital importance in both fundamental research and industrial applications while limited by complex reaction network and suffering from low efficiency. In this study, Ce(OH)SO 4 · x H 2 O was chosen as a probe to systematically investigate the C–H bond activation and C–C bond rupture as a function of various reaction parameters, including the reactant/product concentrations, catalyst applied, reaction temperatures, acidic concentrations etc, and found that bi-molecule of C 6 H 12 was probably involved in both C–H bond rupture and C–C bond cleavage and both were controlled by one deprotonation elementary step with ·O 2 – and h + as the key active components, which were supported by parity fittings and primary KIEs determined. In addition, the C–C bond rupture was found to be mainly following C 6 H 10 O to ε-caprolactone and further to linear acids reaction path. Hopefully, this study could help people find/optimize reaction systems in selective hydrocarbon upgradings.
研究领域:
化学工程
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有机化学
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催化
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Yi Wu,Anqi He,Da Li,Limin Yang,Yizhuang Xu,Yukihiro Ozaki,Isao Noda
This study investigates single-crystal structures of Lu3+/erythritol and nine rare earth–glycerol complexes, revealing deprotonation of normally inert OH groups via μ2-bridging (so-called DIOμ2 phenomenon). The pH drops upon alditol addition correlate with the deprotonation extent, showing increased deprotonation with decreasing lanthanide ionic radius (lanthanide contraction) and exceptionally high deprotonation for Sc3+. In all the rare earth/alditol complexes with the DIOμ2 phenomenon, two μ2-bridges merge into an M2O2 cluster (M is a rare earth ion) that is not very stable due to the Coulombic repulsion between two M3+ and between two O–. To stabilize the M2O2 cluster, the formation of more auxiliary five- and six-membered chelating rings between rare earth ions and alditol ligands is needed. Increment of the number of auxiliary five- and six-membered chelating rings favors the DIOμ2 reaction. This is the reason why the DIOμ2 reaction shows a progressively enhanced tendency when the alditol ligands change from myo-inositol to glycerol to erythritol and galactitol. The reaction is endothermic, as an increased temperature enhances deprotonation. The above results may be useful in the rational design of catalysts that efficiently activate inert OH bonds and facilitate related chemical processes.
研究领域:
无机化学
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配位化学
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晶体学
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物理化学
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催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Water Process Engineering
·
2024
·
IF 6.3
Yang Li,Shuijing Wang,Hengming Huang,Jiahui Kou,Chunhua Lu,Zhongzi Xu,Jinhua Ye
Faster OH − transfer for efficient adsorption on catalysis is key to accelerating the oxygen evolution reaction (OER). The diffusion of OH − in electrolyte mainly involves two mechanism which is dependent on the water coordination number (CN): Grotthuss diffusion (4 CN) and vehicular diffusion (5 CN). The Grotthuss diffusion is much faster but the vehicular diffusion of OH − is predominant in the electrolyte. Herein, negatively charged kaolin, which are simply dispersed in the electrolyte, are utilized to provide surface electrostatic attraction to H 2 O and repulsion to OH − to reduce the OH − CN from 5 to 4 for rapid Grotthuss diffusion. This contributes to the accelerated OH − adsorption which facilitates the charge transfer, the formation and the deprotonation of *OOH leading to enhanced OER performance. The OH − CN recovery from 4 to 5 is proved quite slow after leaving the kaolin surface, breaking the limitation that kaolin must be on the catalyst surface. This strategy exhibits universality for various electrocatalysts with reduced overpotential by 10–246 mV at 10 mA cm −2 . We provide a clean, simple and low-cost way to promote the industrial development of alkaline water electrolysis.
研究领域:
电化学
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材料科学
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催化
·
能量转换
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED MATERIALS
·
2025
·
IF 26.8
Mengjie Wang,Yang Hong,Wenbin He,Qixiang Zhang,Gengchen Yu,Jia Liu,Chen Chen,Li Wen,Dan-Dan Wu,Yongfa Cheng,Chaofeng Zhang,Yanan Ma,Siliang Wang,Yang Yue
Achieving efficient ion transport in thick electrodes remains a fundamental challenge in electrochemical systems with high energy density, primarily due to prolonged diffusion pathways and poorly integrated architectures. Leveraging the nanoconfinement effect, (sub)nanoscale channels can significantly accelerate ion transport kinetics to maximize electrochemical performance. Inspired by the hierarchical network structure of bamboo membrane, a gradient nanoconfined MXene electrode (GNC-MX) is designed, where multiscale interlayer spacing is coupled with in-plane mesopores that bridge adjacent nanoconfined channels, enabling synergistic vertical and horizontal ion migration. Finite element simulations and density functional theory calculations reveal the synergistic optimization mechanism of ion transport via the gradient nanoconfined channels and in-plane mesopores. Compared to pristine MXene, GNC-MX electrodes exhibit substantially enhanced ion transport kinetics and charge storage performance. To optimize the nanoconfined channels, an in situ deprotonation-reprotonation strategy is introduced to strengthen electrostatic repulsion and weaken hydrogen bonding and van der Waals interactions of the MXene interlayer, enabling quasi-permanent expansion of ion transport channels. Furthermore, a scalable group-welding method is developed to fabricate 400 µm-thick electrodes with an ultrahigh areal capacitance of 20.7 F cm −2 , surpassing current MXene-based electrodes. This work provides a scalable and tunable biomimetic platform for advanced ion nanoconfinement in energy storage systems.
研究领域:
材料科学
·
电化学
·
纳米技术
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储能
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计算物理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
iScience
·
2022
·Vol. 25
·期 12
·105669-105669
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IF 6.107
Junli Chao,Yuanyuan Yue,Ke Wang,Xiaohui Guo,Chunying Sun,Yue Xu,Jianming Liu
A concise copper-catalyzed oxidative dehydrogenative dearomatization of indole derivatives for the direct synthesis of spirocyclic indolenines containing fluorene and indeno[2,1- b ]indole groups has been established. The utility of this method has also been successfully accomplished by dual oxidative dehydrogenative dearomatization to deliver the desired spirocyclic indolenines containing fluorene groups. According to mechanistic analyses, the C-H cleavage of the phenyl ring was not implicated in the rate-limiting phase. This transformation underwent a single-electron-transfer oxidation by copper(II) catalyst to afford a radical-cation intermediate, yielding the final product by nucleophilic attack and dual deprotonation.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）