Green Energy & Environment
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2022
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IF 12.781
Bolin Wang,Chunxiao Jin,Shujuan Shao,Yuxue Yue,Yuteng Zhang,Saisai Wang,Renqin Chang,Haifeng Zhang,Jia Zhao,Xiaonian Li
Rational design of catalytic sites to activate the C C bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by controlling the impregnation solutions. The π electrons flowing from acetylene to Cu site are facilitated over the electron-deficient Cu sites, achieving high activation of C C bond. The contradiction between the increased activation of acetylene required for enhanced catalytic activity and the resistance of Cu site to reduction by acetylene required for maintaining catalytic stability can be balanced by establishing strong interactions of Cu site with pyrrolic-N species. The catalytic activity displays a volcano shape scaling relationship as a function of Cu particle size. Tribasic copper chloride is concomitantly generated with the construction of electron-deficient Cu sites. The H–Cl bond of HCl can be activated over the tribasic copper chloride, accelerating the surface reaction of vinyl chloride production. This strategy of inducing electron deficiency provides new insight into the rational design of catalysts for the synthesis of vinyl chloride with a high catalytic performance.
研究领域:
化学催化
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材料科学
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工业化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
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IF 20.2
Ganghua Zhou,Yun Chen,Gaoran Chen,Hangmin Xu,Weiqin Yin,Bin Wang,Xingwang Zhu,Xin Ning,Paul K. Chu,Xiaozhi Wang,Hui Xu
Metal-organic frameworks (MOFs) with abundant pores are excellent adsorbents for metal ions. However, the subsequent treatment of used MOFs and their reutilization still lack promising solutions. Herein, the surface-restructured Mn-doped Cu 2 O (RM-Cu 2 O) catalyst containing asymmetric Mn−Cu sites is prepared by glucose reduction using the spent Cu-based MOF (HKUST-1) as the precursor. The RM-Cu 2 O catalyst shows good potential in tunable photocatalytic syngas (CO and H 2 ) production in a pure water system. The syngas ratios can be tuned from ∼1:2 to ∼1:1 by increasing CO production. DFT calculations and photoelectrochemical tests confirm that the asymmetric Mn−Cu sites on the RM-Cu 2 O catalyst accelerate the photogenerated charge transport and optimize CO 2 adsorption and activation. In situ irradiation X-ray photoelectron spectroscopy is conducted to investigate the dynamic charge transport and reactions on the RM-Cu 2 O catalyst. Based on in situ Fourier transform infrared spectroscopy and simulations, the mechanism of photocatalytic syngas production is elucidated. This work provides a promising solution for the resource utilization of the spent MOFs-based adsorbents and photocatalytic energy development.
研究领域:
材料科学
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能源化学
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 42
·23817-23827
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IF 12.732
Manman Feng,Xuemei Wu,Huiyuan Cheng,Zihao Fan,Xiangcun Li,Fujun Cui,Shuai Fan,Yan Dai,Guangping Lei,Gaohong He
The diatomic catalysts (DACs) provide a new strategy for efficient catalysis of CO2 reduction reaction (CO2RR) owing to their maximum atomic utility and more flexible active sites. However, it is still challenging to precisely design heteronuclear diatomic active centers and understand the coordination mechanism of binary sites at the atomic level. Herein, a nitrogen-doped carbon matrix with precisely controlled Fe–Cu diatom sites is synthesized through a metal–organic framework. The as-obtained Fe/Cu–N–C catalyst exhibits an excellent CO faradaic efficiency (>95% over a wide potential range of −0.4 to −1.1 V vs. RHE, 99.2% at −0.8 V vs. RHE), a high turnover frequency (5047 h−1 at −1.1 V vs. RHE), and a low overpotential (50 mV), thus outperforming most reported atomically dispersed catalysts. Further density functional theory calculations indicate that the synergy between Fe–Cu diatoms causes rapid charge transfer and effectively adjusts the position of the d-band center, which reduces the energy barriers for *COOH formation and *CO desorption. This work provides a new approach for advancing universal synthesis strategies to construct heteronuclear diatomic catalysts and explore synergistic effects.
研究领域:
材料科学
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催化化学
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能源转换
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DOI
高影响因子
ACS Nanoscience Au
·
2024
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IF 4.8
Dan Luo,Zhiheng Xie,Shuangqun Chen,Tianyi Yang,Yalin Guo,Ying Liu,Zhouhao Zhu,Liyong Gan,Lingmei Liu,Jianfeng Huang
Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu–Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu–Ag hybrids exhibit a notable enhancement (2–4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.
研究领域:
化学工程
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电催化
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材料科学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2020
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IF 10.652
Ying Liu,Hongye Bai,Qianxiao Zhang,Yajie Bai,Xuliang Pang,Fagen Wang,Yingchen Yang,Jinrui Ding,Weiqiang Fan,Weidong Shi
Photoelectrochemical N 2 reduction reaction (PEC NRR) into chemical energy source is a promising technique for solving environmental challenges and the energy crisis, which depends on the exploration of p-type photocathodes. Cu 2 O is a p-type semiconductor, which can be applied as a photocathode for PEC NRR. However, the adsorption and activation ability of N 2 over the pristine Cu 2 O is still not ideal, causing the overall efficiency far below the theoretical value. In this work, we first proposed a feasible strategy to in-situ modify the surface of Cu 2 O with Cu-MOF, and the Cu-MOF/Cu 2 O heterostructure exhibited the significantly boosted NH 3 production rate (7.16 mmol/m 2 /h). The ultra-thin Cu-MOF film takes a nature of porous structure and unsaturated Cu sites, contributing to a favorable interface environment for the adsorption and activation of N 2 . The N 2 temperature programmed desorption and contrast photocurrent curves revealed the desirable selectivity for PEC NRR, and the isotope NMR further confirmed the accuracy of NH 3 evolution process. Therefore, the organic–inorganic hybrid systems built from Cu-MOF and Cu 2 O would offer a new insight for establishing the efficient PEC NRR system.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
Nano-Micro Letters
·
2023
·Vol. 15
·期 1
·1-15
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IF 26.6
Li Minhan,Zhang Fangzhou,Kuang Min,Ma Yuanyuan,Liao Ting,Sun Ziqi,Luo Wei,Jiang Wan,Yang Jianping
Electrochemical reduction of CO 2 into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO 2 capture and utilization, resulting from their high catalytic activity and selectivity. The mobility and accessibility of active sites in Cu-based catalysts significantly hinder the development of efficient Cu-based catalysts for CO 2 electrochemical reduction reaction (CO 2 RR). Herein, a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride (g-C 3 N 4 ) as the active sites for CO 2 -to-CH 4 conversion in CO 2 RR. By regulating the coordination and density of Cu sites in g-C 3 N 4 , an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH 4 Faraday efficiency of 49.04% and produces the products with a high CH 4 /C 2 H 4 ratio over 9. This work provides the first experimental study on g-C 3 N 4 -supported single Cu atom catalyst for efficient CH 4 production from CO 2 RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO 2 RR by engineering Cu active sites in 2D materials with porous crystal structures.
研究领域:
化学
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材料科学
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电化学
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环境科学
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产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2025
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IF 6.9
Zong Li,Kaili Ni,Yifei Wang,Yuan Rui,Miaohui Wang,Haiping Lin,Peipei Huang,Qing Li
Achieving high activity and selectivity for multi-carbon (C 2+ ) products on copper-based catalysts at ampere-level current densities is important for advancing industrial electrochemical CO 2 reduction reaction (eCO 2 RR). However, oxidative copper species are prone to reduction to metallic copper at high reduction potentials, causing the decline of selectivity and stability for C 2+ products. Herein, we report that Cucurbit[6]uril (CB[6])-modified copper nanoparticles promote eCO 2 RR via stabilizing Cu + sites at ampere-level current densities. The Cu-CB[6]-3 catalyst exhibited the highest C 2+ productivity with a faradaic efficiency of 72.2 ± 1.0 % at a current density of 1.0 A cm −2 , and the corresponding potential was −1.2 V vs. RHE. Detailed systematical spectroscopic analyses revealed that the main reason for boosting the C–C coupling is that the strong coordination interaction and molecular-level confinement of CO 2 and reaction intermediates of CB[6] can not only stabilize Cu + at higher current densities, but also accelerate the reaction kinetics. Simultaneously, the hydrophobic inner cavity and hydrophilic outer surface of CB[6] molecules ensure the smooth progress of eCO 2 RR while suppressing the hydrogen evolution reaction, resulting in high C 2+ selectivity and long-term stability. This work provides an approach to design highly efficient catalysts for industrial eCO 2 RR.
研究领域:
催化
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电化学
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材料科学
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化学工程
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纳米技术
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产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-22
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IF 14.7
Bai Mingru,Wang Ting,Xing Zhenyu,Huang Haoju,Wu Xizheng,Adeli Mohsen,Wang Mao,Han Xianglong,Ye Ling,Cheng Chong
The clinical treatments of maxillofacial bone defects pose significant challenges due to complex microenvironments, including severe inflammation, high levels of reactive oxygen species (ROS), and potential bacterial infection. Herein, we propose the de novo design of an efficient, versatile, and precise electron-donable heterojunction with synergetic Ru-Cu pair sites (Ru-Cu/EDHJ) for superior biocatalytic regeneration of inflammatory mandible defects and pH-controlled antibacterial therapies. Our studies demonstrate that the unique structure of Ru-Cu/EDHJ enhances the electron density of Ru atoms and optimizes the binding strength of oxygen species, thus improving enzyme-like catalytic performance. Strikingly, this biocompatible Ru-Cu/EDHJ can efficiently switch between ROS scavenging in neutral media and ROS generation in acidic media, thus simultaneously exhibiting superior repair functions and bioadaptive antibacterial properties in treating mandible defects in male mice. We believe synthesizing such biocatalytic heterojunctions with exceptional enzyme-like capabilities will offer a promising pathway for engineering ROS biocatalytic materials to treat trauma, tumors, or infection-caused maxillofacial bone defects.
研究领域:
生物医学工程
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材料科学
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生物材料
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组织工程
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炎症生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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