Catalysis Science & Technology
·
2024
·
IF 4.4
Ling Ding,Lou Gao,Di Pan,Ke Du,Jiayu Yu,Wanyi Li,Yahong Zhang,Yi Tang
The utilization of racemic lactic acid (rac-LA) produced via chemocatalytic conversion for polylactic acid (PLA) synthesis remains limited due to the formation of undesired mesomeric lactide (meso-LD), a by-product that arises during the conversion process. This study proposes the use of shape-selective H-Beta zeolite to reduce the formation of meso-LD in lactide (LD) by leveraging its selectivity towards different lactic dimers (L2A) in a one-step catalytic conversion of rac-LA to LD. Experimental results from various LA solutions with different L2A content indicate that the L2A content is critical for maximizing the selectivity of racemic lactide (D/L-LD), thus confirming the shape-selective nature of H-Beta zeolite towards L2A. Additionally, it is found that increasing the reaction temperature and employing structurally reconstructed H-Beta zeolite with more regularized channels as a catalyst can further decrease meso-LD formation, and a LD yield of 60% with a D/L-LD/meso-LD ratio of 2.26 can be achieved under optimal catalyst and reaction conditions. Despite the coexistence of D/L-LD and meso-LD in the final product, this study marks a significant step towards controlling the stereoisomer distribution of LD synthesized from rac-LA derived from chemical conversion.
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ChemistrySelect
·
2025
·Vol. 10
·期 7
·e202405464
·
IF 2
Kun Jia,Peng Jia
Graphical The asymmetric activation of anhydrous methanol molecules is realized by exogenous protons, the position and protonation position of asymmetric activation are determined, and the C─H bonding energy and reaction activation energy of some methanol molecules are reduced, and the asymmetric regulation of the non-oxidation dehydrogenation reaction process of anhydrous methanol molecules was realized. The activation of C─H bonds under mild conditions is a crucial step in the conversion of organic molecules. However, the simultaneous activation of C─H bonds in methanol can result in excessive oxidation, thereby diminishing the selectivity for formaldehyde production. We achieved selective activation of the C─H bonds in methanol under mild conditions by adjusting the proton concentration in an anhydrous methanol solution, which significantly enhanced the dehydrogenation rate of methanol. Additionally, we constructed related molecular models to identify the sites of asymmetric oxidation, providing new insights for further studies on C─H bond activation.
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ACS Catalysis
·
2024
·
IF 11.3
Zaixiang Xu,Fengcang Zhou,Hanchi Chen,Jianguo Wang
The regeneration of NAD(P)H and its analogues is crucial for biocatalytic processes. However, despite the efficiency of enzymatic catalysis in regenerating NAD(P)H, the sustainability of enzymes is often compromised, particularly under extreme catalytic conditions. Moreover, artificial cofactors may present advantages in certain reactions due to their stability and versatility, yet the substrate specificity of enzymes poses significant challenges to their regeneration through the enzymatic method. Therefore, it is imperative to develop a highly stable regeneration method that can be adapted to both natural and artificial cofactors. In this work, employing potassium-ion-doped carbon nitride (ionCN-0.2) as a catalyst not only achieves high-efficiency photocatalytic regeneration of NAD(P)H, comparable to that of glucose dehydrogenase (GDH), but also a remarkable ability to regenerate nicotinamide analogues. This enhanced performance stems from the tunable negative ζ-potential, which effectively adsorbs the positively charged [Cp*Rh(bpy)H2O]2+ mediator, resulting in enhanced regeneration kinetics of the nicotinamide moiety. The catalyst demonstrates superior performance compared to the reported systems; the optimal regeneration rate reaches 0.55 mmol L–1 gcat–1 min–1 and approaches enzymatic regeneration efficiency. Expanding the reaction conditions to a wider temperature and pH range also confirms the effectiveness and sufficient stability of this photocatalytic system, offering a promising strategy for stable cofactor regeneration in biocatalytic processes.
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Surfaces and Interfaces
·
2024
·
IF 5.7
Zhiwei Zou,Hongxiang Zhang,Xuefeng Pan,Hui Shen,Jianying Yu,Tengfei Guo,Yonghao Wang
Electrocatalytic reduction of nitrate (NO 3 - ) to ammonium (NH 4 + ) is an environment friendly approach for treating nitrogen-containing wastewater. Consequently, electrocatalysts capable of effectively and selectively reducing NO 3 - to NH 4 + receives growing attention. However, Cu-based catalysts demonstrate limited efficiency and the drawback of generating toxic NO 2 - though it is prevalent in the field of electrocatalytic reduction of NO 3 - (NO 3 RR). In this work, a CuNi alloy was synthesized on a Co foil through electrodeposition (marked as CuNi@Co) and its electrocatalytic performance for NO 3 RR was evaluated. XRD, EDS mapping and XPS characterization indicate CuNi exists with alloy state. Electrocatalytic experiments demonstrate that CuNi@Co exhibits an exceptional FE NH3 of 99.12% at -0.64 V (vs. RHE). Importantly, no detrimental NO 2 - generated during NO 3 RR process because the reduction rate from NO 2 - to NH 4 + is faster than that from NO 3 - to NO 2 - . Mechanistic analysis suggests that Cu serves as a ‘reservoir’ to provide electrons to facilitate the reduction of NO 3 - to NO 2 - during NO 3 RR process and the synergistic effect of Ni and Cu promotes more active hydrogen (H*) to participate the reduction process of NO 2 - to NH 4 + not H 2 generation, ultimately improving FE NH3 . This work elucidates the role of electrons and H* in electrocatalytic nitrate reduction to ammonium for CuNi alloy, providing new insights into the reduction process of NO 3 RR for Cu-based materials.
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ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Shiwen Wang,Chuanzhen Ma,Junwei Ding,Kang Zhao,Heng Wang,Hewei Luo,Shide Wu,Shaoming Fang
VO 2 (B) has attracted tremendous attention as a cathode for aqueous zinc-ion batteries (AZIBs), but its low intrinsic electronic conductivity and uncontrolled vanadium dissolution hinder further practical applications. Herein, Zn 0.03 VO 2 , with guest zinc ions preinserted into the tunnel sites, is demonstrated to enhance the conductivity and cyclability of VO 2 (B). The tailored structure, featuring a modulated electronic configuration, offers enlarged ion diffusion tunnels, improved electronic conductivity, and enhanced electrochemical activity, thereby facilitating the reversible de-intercalation of Zn 2+ /H + ions, as confirmed by both experimental results and theoretical calculations. Notably, vanadium dissolution is significantly suppressed due to the chemical pre-insertion of guest zinc, which weakens the interaction between Zn 2+ and host lattice, as well as the homologous ion effect. As a result, Zn 0.03 VO 2 cathode delivers a high capacity of 358 mAh g −1 , particularly at low current density of 0.1 A g −1 , with 85% capacity retention after 300 cycles, excellent rate capability of 175 mAh g −1 at 5 A g −1 , and long cycling stability over 2000 cycles at 20 A g −1 . Moreover, a pseudocapacitive-dominated Zn 2+ /H + co-insertion mechanism is conclusively identified through electrochemical and spectroscopic analyses. This work provides valuable insights into ion-preinserted structural modulation of vanadium oxides for the development of high-performance AZIBs.
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ACS Catalysis
·
2025
·
IF 13.1
Yu-Yang Liu,Shan Xu,Xiao-Xin Li,Run-Han Li,Xin-Ting Cai,Hui-Zhen Zhong,Jiang Liu,Qing Huang,Lei Zhang,Shun-Li Li,Ya-Qian Lan
Developing strategies and photocatalysts for C(sp3)-H bond functionalization under simple and mild conditions is important but challenging. Here, we report two redox heterocluster-based frameworks, named Ni5-PW12 and Ni5-V16, in which the terminal oxygen atoms of polyoxometalates are directly coordinated to metal atoms in metal–organic clusters. Due to the coexisting strong oxidation and reduction capacities, both of these photocatalysts achieve photocatalytic C(sp3)-H bond oxidative imination through combining oxidation of methyl aromatics and reduction of nitro aromatics reactions. The experimental and theoretical results reveal that benefiting from the short distance between the clusters, the rapid charge transfer and mass transfer processes would enhance the photocatalytic reactivity and inhibit side reactions. More importantly, all of the photocatalytic reactions are carried out in mild conditions at room temperature without any additional solvents, photosensitizers, oxidizing or reducing agents, or cocatalysts.
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Joule
·
2020
·
IF 29.155
Anyi Mei,Yusong Sheng,Yue Ming,Yue Hu,Yaoguang Rong,Weihua Zhang,Shulin Luo,Guangren Na,Chengbo Tian,Xiaomeng Hou,Yuli Xiong,Zhihui Zhang,Shuang Liu,Satoshi Uchida,Tae-Woong Kim,Yongbo Yuan,Lijun Zhang,Yinhua Zhou,Hongwei Han
Summary The stability of perovskite solar cells (PSCs) has been considered as the largest obstacle to their commercialization. Herein, we observed that the main failure mechanism for MAPbI 3 perovskite is the escape of methylammonium (MA) iodide at the grain boundaries in an open space or the reconstruction of crystal in a confined small space, as well as the irreversible long-distance ionic migration under the multiple actions of light, heat, and electrical bias. Strengthened with bifunctional organic molecular of 5-ammoniumvaleric acid (5-AVA) iodide at the grain boundaries, the MAPbI 3 crystal was localized in the nanoscale, and thus, the decomposition or reconstruction was inhibited and the ionic migration became reversible. As a result, we propose a reliable approach to make PSCs meet stability standards of IEC61215:2016 qualification tests. A printable PSC filled with (5-AVA) X MA 1-X PbI 3 has been working for more than 9,000 h at a maximum power point of 55°C ± 5°C without obvious decay.
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ACS Nano
·
2023
·
IF 17.1
Changhao Zhu,Xuye He,Yun Shi,Zhenkang Wang,Baojiu Hao,Wanhao Chen,Hao Yang,Lifang Zhang,Haoqing Ji,Jie Liu,Chenglin Yan,Jinqiu Zhou,Tao Qian
Despite the numerous advantages of aqueous Zn batteries, their practical application under cryogenic conditions is hindered by the freezing of the electrolyte because the abundance of hydrogen bonds (H-bonds) between H2O molecules drives the aqueous system to transform to an orderly frozen structure. Here, a design of H-bond interactions based on the guiding ideology of “strong replaces weak” is proposed. The strong H-bonds formed between introduced eutectic components and water molecules break down the weak H-bonds in the original water molecule network, which contributes to an ultralow freezing point and a high ionic conductivity of 1.7 mS cm–1 at −40 °C. Based on multiperspective theoretical simulations and tailor-made in situ cooling Raman characterizations, it has been demonstrated that substituting weak H-bonds with strong H-bonds facilitates the structural reshaping of Zn2+ solvation and remodeling of the H-bond network in the electrolyte. Endowed with this advantage, reversible and stable Zn plating/stripping behaviors could be realized at −40 °C, and the full cells display a high discharge capacity (200 mA h g–1) at −40 °C with ∼75% capacity retention after 1000 cycles. This study will expand the design philosophy of antifreezing aqueous electrolytes and provide a perspective to promote the adoption of Zn metal batteries for cryogenic environment large-scale energy storage.
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INTERNATIONAL JOURNAL OF FOOD SCIENCES AND NUTRITION
·
2019
·
IF 2.792
Yuanfeng Wu,Yuke Shen,Ye Zhu,Jothame Mupunga,Ligen Zou,Chao Liu,Shiwang Liu,Jianwei Mao
After consuming broccoli, isothiocyanates can be produced by the hydrolytic action of myrosinase from plant and/or microbiota. Using male C57BL/6 mice, the present study investigated the effects of broccoli ingestion on the myrosinase-like activity, NAD(P)H:quinone oxidoreductase 1 (NQO1) activity, diversity and composition of the gut microbiota. Compared with the control group, continuously feeding raw or hydrolysed broccoli increased the myrosinase-like activities of the colon and caecum contents, and also improved the NQO1 activity of the colon mucosa. Significant difference between the broccoli and control feeding groups were found. 16S rRNA gene sequencing indicated that broccoli ingestion profoundly affected the composition of the gut bacteria community. The correlation between the gut bacterial community composition and microbiota myrosinase-like activity was also studied. However, one type of glucosinolate, sinigrin, had no effect on these activities, indicating that broccoli component(s), other than glucosinolate, had increased the NQO1 and myrosinase-like activities.
研究领域:
营养学
·
微生物学
·
分子生物学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2015
·
IF 2.587
Yujia Xie,Fengyong Zhang,Pingle Liu,Fang Hao,Hean Luo
Direct functionalization of saturated C–H bonds by metalloporphyrin catalysts is among the topical and challenging areas within the chemical industry and synthetic chemistry. In this work, supported CoD(p-Cl)PPCl metalloporphyrin catalysts were prepared and characterized. It has been found that the CoD(p-Cl)PPCl/ZnO catalyst shows better catalytic activity than the supported catalyst (ZrO2, MCM-41, kaolin, Zr(OH)2, and boehmite (BM)) in cyclohexane oxidation with dioxygen. The effects of the reaction pressure, reaction temperature, and reaction time on the catalytic activity were considered by the supported CoD(p-Cl)PPCl/ZnO catalyst. The CoD(p-Cl)PPCl/ZnO catalyst can be facilely recovered and was recycled up to seven times without a significant decrease in catalytic performance. The average cyclohexane conversion and selectivity to KA oil are 10.98% and 84.34%, respectively, and the turnover number is 2.10 × 107.
研究领域:
催化化学
·
有机合成
·
工业化学
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材料化学
·
绿色化学
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Small Methods
·
2026
·
IF 8.7
Xiaochen Feng,Zihao Huang,Mingwei Fang,Meiling Wang,Jinyue Ma,Zewen Wang,Ying Zhu,Lei Jiang
Electrochemical CO 2 reduction (CO 2 RR) to ethanol offers a sustainable route for carbon utilization and energy storage, yet achieving high ethanol selectivity under limited CO 2 availability remains a significant challenge. The central issue is the lack of quantitative understanding of how the interfacial * CO and * H intermediates jointly govern product selectivity. Here, we establish an interfacial coverage regulation strategy by embedding Cu nanoparticles into an imine-functionalized covalent organic framework (Cu/Im-COF). The imine-rich interface enriches CO 2 adsorption while modulating proton transfer, enabling a balanced surface coverage of * CO and * H, identified as the key selectivity descriptor ( θ *CO/*H ) for ethanol formation. Operando Raman spectroscopy, density functional theory calculations, confirms that an optimized θ *CO/*H stabilizes the * HCCHOH intermediate and lowers its formation barrier. Quantitative integration of Raman features allows direct determination of θ *CO/*H , revealing a volcano-type dependence of ethanol selectivity on this descriptor. A maximum ethanol Faradaic efficiency of 56% is achieved at log( θ *CO/*H ) ≈ 3.0, a current density of 700 mA cm − 2 , and a 15% CO 2 feed. This work establishes θ *CO/*H as a quantitative bridge between intermediate coverage and reaction kinetics, providing a mechanistic framework for rational design of CO 2 RR catalysts with high ethanol selectivity under CO 2 -constrained conditions.
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PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2026
·Vol. 123
·期 9
·e2533803123
·
IF 9.5
Guobin Wen,Haiqi Liang,Shuxuan Liu,Ningce Zhang,Shuai Chen,Guoqiang Shen,Tehua Wang,Ru Chen,Li Tao,Bohua Ren,Shuangyin Wang
Electrochemical hydrogen isotope separation has been constrained for decades by the similar energy barriers of the rate-determining O–H and O–D bond cleavage step in water isotopologues. Herein, we compact H-bond connectivity through screening a series of additives to stimulate electrochemical proton quantum tunneling (QT) behaviors of “through-barrier”, which are virtually impossible for heavier D-relevant motions. The average H-bond length of H2O⋯OH− is 3.4% shorter (2.78 Å) with isopropanol additive at the engineered interface. Fundamentally, QT effects are magnified by selectively promoting proton transfer-involved reactions through strengthening the H-bond and filling the H-bond gap, which are further proved by both experimental Arrhenius plots with near small-curvature tunneling approximation and a stronger proton excursion in path integral molecular dynamics simulations. Hence, a record-high H2O separation factor of 276 is realized at room temperature with a three-order-of-magnitude growth of H/D kinetic isotope effect constant up to 10,165. Significantly, a large-scale multistage reactor is engineered to obtain continuous enrichment of heavy water with a deuterium atomic fraction over 80%.
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