CHEMICAL ENGINEERING JOURNAL
·
2024
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IF 13.3
Fuxia Huang,Zihao Jiao,Feng Wang,Ya Liu,Liejin Guo
Direct photocatalytic CO 2 conversion to C 2 products holds notable potential, but this technology is still limited by the high thermodynamic energy and sluggish kinetics. By introducing Cu in In 4 SnS 8 catalyst, we here developed low S vacancies and chemical reactive sites photocatalysts Cu-In 4 SnS 8 , enabling photocatalytic CO 2 to ethanol with full selectivity. Minor electron paramagnetic resonance peak intensity and large formation energy for S-vacancy suggest Cu introduction suppresses S vacancies formation. Low S vacancies photocatalysts Cu-In 4 SnS 8 possess excellent carrier transfer and separation ability by the steady photoluminescence and transient fluorescence characteristic results. Furthermore, in situ, FTIR measurements confirmed ethanol formation via the presence of the intermediates *COOH, *CO, *OCCO(H), and *OCH 2 CH 3 . Also, theory calculations reveal that Cu efficiently reduces the energy barriers of the rate-limiting steps of *COOH and *COH, and promotes C-C coupling and multi-proton coupled electron transfer processes by co-adsorption and asymmetric charge distribution effects. As a result, the optimized sample achieves 0.73 μmol h −1 CH 3 CH 2 OH generation with full selectivity.
研究领域:
材料科学
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催化化学
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环境科学
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产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2024
·
IF 7.2
Huifang Guo,Yuping Chen,Ying-Zi Han,Qingyuan Wu,Lin Wang,Qinghua Xu,Rong Huo,Xuekun Gong,Jing Sun,Qing Tang,Hui Shen
The catalytic activity of ligand-protected metal nanoclusters is often hindered by the blocking effect of surface ligands, necessitating the creation of more uncoordinated sites to enhance their performance. In this work, we report a strategy for boosting the catalysis of fully ligand-protected silver nanoclusters by anchoring uncoordinated copper sites. By employing a bulky ligand, 2,4,6-triisopropylbenzenethiol, and a copper-functionalized reducing agent, a cluster denoted as Ag14Cu7(PPh3)6(SR)6 (Ag14Cu7, RSH is 2,4,6-triisopropylbenzenethiol) has been prepared. The structure of Ag14Cu7 closely resembles that of the previously reported Ag14(SPh(CF3)2)12(PPh3)4(DMF)4 (Ag14), whose geometric structure describes the addition of seven Cu atoms onto the Ag14 moiety, one at the center and another six on the surface. To our surprise, the presence of extra uncoordinated copper sites on the surface significantly enhances the catalytic activity of Ag14Cu7 in hydrogenation reactions. This work not only reports a model system to shed light on the significance of surface uncoordinated metal sites in cluster catalysis but also offers an effective strategy utilizing bulky ligands and functionalized reducing agents to generate additional uncoordinated sites on the surface of metal nanocluster catalysts.
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
Yin Jinwen,Wang Jing,Sun Mingzi,Yang Yajie,Lyu Jia,Wang Lei,Dong Xinglong,Ye Chenliang,Bao Haibo,Guo Jun,Chen Bo,Zhou Xichen,Zhai Li,Li Zijian,He Zhen,Luo Qinxin,Meng Xiang,Ma Yangbo,Zhou Jingwen,Lu Pengyi,Wang Yunhao,Niu Wenxin,Zheng Zijian,Han Yu,Zhang Daliang,Xi Shibo,Yuan Ye,Huang Bolong,Guo Peng,Fan Zhanxi
Prussian blue analogs (PBAs), as a classical kind of microporous materials, have attracted substantial interests considering their well-defined framework structures, unique physicochemical properties and low cost. However, PBAs typically adopt cubic structure that features small pore size and low specific surface area, which greatly limits their practical applications in various fields ranging from gas adsorption/separation to energy conversion/storage and biomedical treatments. Here we report the facile and general synthesis of unconventional hexagonal open PBA structures. The obtained hexagonal copper hexacyanocobaltate PBA prisms (H-CuCo) demonstrate large pore size and specific surface area of 12.32 Å and 1273 m 2 g − 1 , respectively, well exceeding those (5.48 Å and 443 m 2 g − 1 ) of traditional cubic CuCo PBA cubes (C-CuCo). Significantly, H-CuCo exhibits much superior gas uptake capacity over C-CuCo toward carbon dioxide and small hydrocarbon molecules. Mechanism studies reveal that unsaturated Cu sites with planar quadrilateral configurations in H-CuCo enhance the gas adsorption performance.
研究领域:
材料科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
Lu Yuxuan,Yue Feng,Liu Tianyang,Huang Yu-Cheng,Fu Feng,Jing Yu,Yang Hengquan,Yang Chunming
The synergistic Cu 0 -Cu + sites is regarded as the active species towards NH 3 synthesis from the nitrate electrochemical reduction reaction (NO 3 - RR) process. However, the mechanistic understanding and the roles of Cu 0 and Cu + remain exclusive. The big obstacle is that it is challenging to effectively regulate the interfacial motifs of Cu 0 -Cu + sites. In this paper, we describe the tunable construction of Cu 0 -Cu + interfacial structure by modulating the size-effect of Cu 2 O nanocube electrocatalysts to NO 3 - RR performance. We elucidate the formation mechanism of Cu 0 -Cu + motifs by correlating the macroscopic particle size with the microscopic coordinated structure properties, and identify the synergistic effect of Cu 0 -Cu + motifs on NO 3 - RR. Based on the rational design of Cu 0 -Cu + interfacial electrocatalyst, we develop an efficient paired-electrolysis system to simultaneously achieve the efficient production of NH 3 and 2,5-furandicarboxylic acid at an industrially relevant current densities (2 A cm −2 ), while maintaining high Faradaic efficiencies, high yield rates, and long-term operational stability in a 100 cm 2 electrolyzers, indicating promising practical applications.
研究领域:
材料科学
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电化学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2025
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IF 12.1
Teng Zhang,Xueya Dai,Yihong Yu,Xin Cui,Yunlong Li,Gaowu Qin,Wei Qi,Song Li
Electrochemical conversion of CO 2 into value-added multi-carbon products is highly attractive for CO 2 utilization using sustainable electricity energy. However, achieving high ethanol selectivity of copper-based catalysts remains challenging due to the competing side reactions such as ethylene formation. Herein, a novel electrocatalyst, PANI-Ag/Cu-OH is reported, comprising of polyaniline-supported silver single atoms coupled with hydroxyl-modified copper clusters. Tandem reduction of CO 2 into ethanol with a high selectivity is realized by coupling CO formation on Ag site and further reduction on hydroxylated Cu sites. The synergistic approach enables a high Faradaic efficiency of 68.9% for ethanol with a current density of −263.8 mA cm −2 at −0.78 V versus RHE in alkaline media. CO-TPD and in situ infrared spectra studies reveal that strong CO adsorption and Cu + species stabilized by hydroxyl groups are crucial for asymmetric C–C coupling and stabilization of the ethanol intermediates, leading to the enhanced ethanol selectivity.
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
PubMed
高影响因子
TALANTA
·
2025
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IF 6.1
Dan Hu,Yalin Zhao,Xinyue Wei,Shijuan Song,Xinyue Lei,Fengchun Yang,Xin Zhang
Glyphosate (GLY) is a widely used herbicide, and its potential health and environmental risks require the establishment of efficient residue detection techniques. In the design of photoelectrochemical (PEC) sensors based on CuTCPP, it is necessary to increase the visible light absorption efficiency and promote the separation of photogenerated electron-hole, as well as balance the adsorption and desorption of GLY to maintain excellent reversibility and responsiveness. In this work, the synergistic effect of type-II heterojunction g-C 3 N 4 /CuTCPP on the dynamic conversion of copper sites under illumination and applied voltage is explored for the first time and a portable glyphosate detection device is designed to meet the practical application requirements. By constructing g-C 3 N 4 /CuTCPP heterostructure, a large number of Cu + sites are generated to promote the desorption of GLY. At the same time, Cu + is oxidized by applied voltage, which promotes the adsorption of GLY and enhances the electrochemical signal response. The proposed PEC sensor exhibits a linear range from 1.0 pM to 0.1 mM and a detection limit of 0.009 pM. It can also be used to detect the GLY content in campus ponds and suburban field streams, showing satisfactory analytical performance, demonstrating the promising potential of g-C 3 N 4 /CuTCPP on the dynamic conversion of copper sites under light and applied voltage synergistically for optimizing the adsorption/desorption of GLY to boost the PEC detecting performance.
研究领域:
环境科学
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分析化学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2020
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IF 10.652
Zhiyue Dong,Liang Zhang,Jiang Gong,Qiang Zhao
Covalent organic frameworks (COFs) nanostructures capable of efficient visible light absorption, complete holes-electrons separation, and reactant enrichment remain a synthetic challenge for advanced photocatalysts. Herein, we rationally design a novel Cu-coordinated terpyridyl-based, 2D lamellar COF-909(Cu) nanorods. The coordinated single Cu sites not only dramatically enhance the visible light absorption and achieve the complete electrons-holes separation, but also provide the specific binding sites to enrich N/O-containing organic toxicants. The laminar arrangement and 1D nanochannel of COF-909(Cu) nanorods shorten the transfer distance of electrons to the active sites. As a proof of concept, it shows excellent performance in the photocatalytic degradation of sulfamethoxazole, which surpasses the-state-of-art photocatalysts. Density functional theory calculations confirm the structure-function relationship between the single Cu sites and the complete electrons-holes separation as well as strong binding sites for target molecules.
研究领域:
材料科学
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环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Hailun Geng,Shengying Zhao,Minghui Tan,Jie Yao,Hao Song,Chuang Gu,Tiecheng Shang,Wenzhong Shen,Guohui Yang,Noritatsu Tsubaki
Metal-zeolite catalysts are widely utilized in various industrial reactions. However, the size, loading, and reduction of metal species are interdependent, complicating efforts to optimize their catalytic performance. In this study, we introduce a novel strategy for the synthesis of metal-zeolite catalysts, termed the multi-amino effect. This new method involves functionalizing zeolite surfaces with aliphatic diamines, such as 1,3-diaminopropane, to leverage the multifaceted properties of the amino group. 1,3-diaminopropane is anchored to the zeolite framework via one terminal amino group, while the other terminal amino group facilitates the efficient loading and dispersion of Cu species through interaction with Cu 2+ . The multi-amino groups present in the structure enable the in situ multi-stage release of abundant NH 3 during calcination, facilitating the self-reduction of Cu species to generate a high proportion of Cu + and Cu 0 species. Notably, the Cu-MOR catalyst prepared by this approach exhibits a significantly improved methyl acetate production rate, which is 1.56 times higher than that of the traditional hydrogen reduction method and 1.37 times greater than that of the ammonia pool method, owing to the abundance of highly dispersed and highly active Cu sites (Cu + :Cu 0 ≈ 1:1). This multi-amino effect strategy will help to develop more efficient and tunable metal-zeolite catalysts, driving advances in industrial processes such as sustainable chemical production and energy conversion, with significant improvements in both catalytic activity and cost-effectiveness.
研究领域:
催化化学
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材料科学
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工业化学
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能源转化
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绿色化学
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多相催化
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无机功能材料
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Jie Liu,Lin Yang,Wenju Jiang,Zhongde Dai,Lu Yao,Junfeng Zheng,Xingjian Wang
In this study, the Cu/C@Zeolite catalysts with carbon-zeolite bifunctional support was developed by using the zeolite-induced one-pot homogeneous synthesis of CuBTC composite (CuBTC@Zeolite). Three different zeolites (ZSM-5, 13X, NaY) and the activation conditions were discussed. Originating from the defective structure of CuBTC in the composite and its interactivity with the zeolite, compared to Cu/C, the Cu/C@zeolite catalysts had the hierarchical pore system, a higher content of oxygen vacancies, stronger redox properties, and more active Cu sites with smaller particle sizes and more Cu + /Cu 2+ coexisting valence states, in synergy with acid sites, all of these contributing to the improved catalytic activity for VOCs oxidation removal. The activity of toluene catalytic oxidation indicated by T 90 was in the order of Cu/C@NaY (268.5 °C) > Cu/C@ZSM-5 (280.0 °C) > Cu/C@13X (287.0 °C) > Cu/C (320.0 °C). They also performed a better activity for acetone and ethyl acetate oxidation, obtaining the lowest T 90 at 217.0 and 231.5 °C respectively when the Cu/C@NaY used. Moreover, the Cu/C@NaY and Cu/C@ZSM-5 performed good water resistance and stability, suggesting the potential in practical application scenarios. These findings underscored the potential of Cu/C@Zeolite catalysts for addressing complex VOCs in simultaneous catalytic oxidation.
研究领域:
环境科学
·
催化化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Da Wan,Yilei Zhang,Sizhen He,Huizhu Cai,Xue Zhang,Qi Hu,Hengpan Yang,Chuanxin He
The electrocatalytic NO 3 - reduction reaction (NO 3 - RR) proves the feasibility for the synthesis of NH 3 under mild conditions, yet it still faces challenges such as poor product selectivity and low reaction rates. Inspired by biological enzymes that exhibit both high selectivity and superior reaction rates, we designed an enzyme-mimetic catalyst for highly efficient NO 3 - RR. Specifically, mesoporous carbon nanofibers (CNFs) act as confined microenvironments for the enrichment of reactants, and the synergistic catalysis of Cu nanoclusters (Cu NCs) and Cu single atoms (Cu SAs) can match the complex reaction pathways of multiple intermediates and multiple proton/electron transfers. Consequently, the as-synthesized Cu NCs&SAs @CNFs catalyst achieves a remarkable NH 3 Faradaic efficiency (FE) of 97.23 % and a high yield rate of 31.45 mg h −1 cm −1 . Additionally, we employed the Cu NCs&SAs @CNFs as a cathode to assemble a Zn-NO 3 - battery, the system maintains a stable open circuit voltage of 1.36 V over 10 h continuous operation. This work combines the regulation of active sites and tuning of microenvironments, which might provide some insights for designing enzyme-mimicking catalysts in various electrocatalytic systems.
研究领域:
电催化
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材料科学
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纳米技术
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能量转换
·
环境修复
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-10
·
IF 14.7
Zhu Jiawei,Zhang Yu,Chen Zitao,Zhang Zhenbao,Tian Xuezeng,Huang Minghua,Bai Xuedong,Wang Xue,Zhu Yongfa,Jiang Heqing
Cu-oxide-based catalysts are promising for CO 2 electroreduction (CO 2 RR) to CH 4 , but suffer from inevitable reduction (to metallic Cu) and uncontrollable structural collapse. Here we report Cu-based rock-salt-ordered double perovskite oxides with superexchange-stabilized long-distance Cu sites for efficient and stable CO 2 -to-CH 4 conversion. For the proof-of-concept catalyst of Sr 2 CuWO 6 , its corner-linked CuO 6 and WO 6 octahedral motifs alternate in all three crystallographic dimensions, creating sufficiently long Cu-Cu distances (at least 5.4 Å) and introducing marked superexchange interaction mainly manifested by O-anion-mediated electron transfer (from Cu to W sites). In CO 2 RR, the Sr 2 CuWO 6 exhibits significant improvements (up to 14.1 folds) in activity and selectivity for CH 4 , together with well boosted stability, relative to a physical-mixture counterpart of CuO/WO 3 . Moreover, the Sr 2 CuWO 6 is the most effective Cu-based-perovskite catalyst for CO 2 methanation, achieving a remarkable selectivity of 73.1% at 400 mA cm −2 for CH 4 . Our experiments and theoretical calculations highlight the long Cu-Cu distances promoting *CO hydrogenation and the superexchange interaction stabilizing Cu sites as responsible for the superb performance.
研究领域:
材料科学
·
电化学
·
催化
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可持续能源
✓ 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）