APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Ting Wang,Fuli Sun,Shoujie Liu,Guilin Zhuang,Benxia Li
Supported Cu single-atom (Cu-SA) catalysts have exhibited unique activity and selectivity in CO 2 reduction, but they generally suffer from the easy transformation of active Cu δ+ into inactive Cu 0 . Herein, porous TiO 2 supported Cu single atoms (Cu-SAs/TiO 2 ) photocatalyst was fabricated and dioxygen (O 2 ) enhanced photocatalytic CO 2 reduction performance of Cu-SAs/TiO 2 was investigated by in-situ characterizations and theoretical calculations. The results showed that both activity and stability of Cu-SAs/TiO 2 photocatalyst could be improved by feeding a small amount of O 2 (117.6 ppm) in the reaction system. The competitive electron transfer to O 2 on Cu-SAs/TiO 2 maintained dynamic stability of Cu δ+ active sites, and O 2 -derived *OOH species lowered the formation energy barrier of key intermediate *COOH as well as delivered *H species for accelerating intermediates protonation process. Total yield rate of CH 4 and CO reached 34.64 μmol·g cat ·h −1 for CO 2 photoreduction over Cu-SAs/TiO 2 after introducing 117.6 ppm O 2 , accompanied by enhanced durability.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Fangxian Wang,Junwei Yang,Shihao Li,Junwen Liang,Yuwei Wang,Rong Du,Bo Zhou,Qiong Liu,Changping Li
Bromate is a commonly identified carcinogenic and genotoxic disinfection byproduct in water. Electrochemical debromination is an environmentally friendly and effective approach but it often suffers the limited reducing atomic H (H*) ability and high metal catalyst dosage. In this study, a unique composite catalyst comprised of ultra-low loading Cu single atoms (0.016 wt%) and Fe 2 O 3 nanoparticles supported on a Nb 2 C MXene (denoted as Cu 0.2 /Fe 0.1 /Nb 2 C) was synthesized by one-step high-temperature molten salt method. The Cu 0.2 /Fe 0.1 /Nb 2 C significantly outperformed the Nb 2 C, Cu 0.2 /Nb 2 C and Fe 0.1 /Nb 2 C counterparts in the electrochemical debromination with a 94.2 % removal efficiency of bromate. It is revealed that the introducing of Cu single atoms, efficiently promotes the adsorption of H* and inhibition of competitive H 2 evolution. The incorporation of Fe 2 O 3 nanoparticles significantly increased the electronic metal-support interaction effect between the metal components and Nb 2 C, thereby forming a noticeable electronic cloud bridge to facilitate efficient charge transfer. Ultimately, the synergistic interplay between Cu single atoms and Fe 2 O 3 nanoparticles plays a crucial role in achieving the remarkable removal performance of bromate. This work not only presents a significant instance of a synergistic catalyst involving metal single atoms and metal nanoparticles for effective electrochemical debromination but also advances the understanding of the electronic metal-support interaction.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2022
·Vol. 14
·期 42
·15889-15896
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IF 8.307
Yuxiang Ma,Yumin Zhang,Yiwen Ma,Tianping Lv,Bin Xiao,Xinya Kuang,Xiyu Deng,Jin Zhang,Jianhong Zhao,Qingju Liu
Single atom catalysts (SACs) have an extremely high atom utilization and distinctive structures and properties in the field of photocatalysis. However, the premise of conducting scientific research and applications is still the stability and catalytic activity of single atoms on suitable substrates. Metal organic frameworks (MOFs), as one of the most suitable single-atom substrates, have tunable internal structures, unsaturated coordination bonds, and high specific surface areas. In this work, Ti-based MOF, MIL-125, was adopted as the precursor to prepare mesoporous Cu-loaded TiO2. During the synthesis of MIL-125, a Cu source was added, and Cu atoms were fixed by partly replacing Ti atoms in the Ti–O octahedron to coordinate with O atoms, resulting in a good dispersity, good stability and high loading amount. Experimental investigations demonstrated that dispersed Cu single atoms act as reaction centres, besides being able to accelerate the transfer of photoelectrons. Under simulated sunlight, the H2 evolution rate of the optimum Cu–TiO2 sample reaches 17.77 mmol g−1 h−1, nearly 101 times higher than that of the pure mesoporous TiO2. The apparent quantum efficiency (AQE) is 20.15% under 365 nm irradiation. This research opens a new thinking to preparing high stability and high activity single atom photocatalysts.
研究领域:
材料科学
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光催化
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能源科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Deyu Qin,Chen Zhang,Fanzhi Qin,Yin Zhou,Danlian Huang,Hou Wang,Hanzhuo Luo,Qi Wang,Lin Tang,Wenwei Li
Developing atomically dispersed metal sites is vital to enhance the activation of peroxymonosulfate (PMS). However, for catalyst systems where single atoms and nanoclusters coexist, how to identify the independent and synergistic effects of atomic sites and investigate the possible coexistence of multiple activation mechanisms still remains a great challenge. Herein, Cu SA /CoO x -CeO 2 catalysts with Cu single atoms and CoO x nanoclusters were fabricated for PMS activation. The introduction of Cu single atoms led to the reconstruction and diversification of catalytic active sites of CoO x -CeO 2 . The synergy between CoO x nanoclusters and neighboring Cu single atoms in Cu SA /CoO x -CeO 2 catalyst led to the 1 O 2 pathway of PMS activation, while the isolated Cu atom induced the Cu(III) oxidation pathway. The introducing of adjacent Cu single atoms caused the redistribution of the site charges in CoO x nanoclusters, which enhanced the charge transfer and promoted the adsorption and activation behavior of PMS molecules. During the evolution of 1 O 2 , the synergistic effect of Cu single atoms and CoO x nanoclusters increased the stability of the reaction intermediate state (*OO*SO 3 ), reducing the total Gibbs free energy change (ΔG) required for 1 O 2 formation. Compared with the cooperative site, the isolated Cu-O4 sites exhibited stronger charge transfer capacity to PMS molecules and were more conducive to the activation of the local substrate electronic structure, facilitating the formation and stabilization of Cu(III)–OH metastable intermediates. Overall, this study demonstrated the importance about the construction of multi-site induced multipath coexisting PMS activation system and the accurate identification of active sites.
研究领域:
环境科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-9
·
IF 16.6
Zhang Li,Yang Xiaoju,Yuan Qing,Wei Zhiming,Ding Jie,Chu Tianshu,Rong Chao,Zhang Qiao,Ye Zhenkun,Xuan Fu-Zhen,Zhai Yueming,Zhang Bowei,Yang Xuan
Understanding the structure-stability relationship of catalysts is imperative for the development of high-performance electrocatalytic devices. Herein, we utilize operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) to quantitatively monitor the evolution of Cu single-atom catalysts (SACs) during the electrochemical reduction of CO 2 (CO 2 RR). Cu SACs are converted into 2-nm Cu nanoparticles through a reconstruction process during CO 2 RR. The evolution rate of Cu SACs is highly dependent on the substrates of the catalysts due to the coordination difference. Density functional theory calculations demonstrate that the stability of Cu SACs is highly dependent on their formation energy, which can be manipulated by controlling the affinity between Cu sites and substrates. This work highlights the use of operando ATR-SEIRAS to achieve mechanistic understanding of structure-stability relationship for long-term applications.
研究领域:
催化
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电化学
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表面科学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Zhongyu Jing,Bonan Liu,Kewen Huang,Yu Fan
Regulating the electronic structure of copper (Cu) active sites is an effective means to improve the electrochemical carbon dioxide reduction (ECO 2 R) performance of Cu single-site catalysts. However, the effect of specific functional groups on the electronic structure of Cu sites in Cu-based catalysts is unknown. In this paper, a novel electron-donating –OCH 3 modified Cu-based Salphen organic framework (Cu-SOF) with the Cu-N 2 O 2 configuration was synthesized by the Schiff base reaction. The –OCH 3 groups served as electron donors to induce electron transfer toward the Cu site, which improved the electrochemical CO 2 reduction (ECO 2 R) performance of Cu-SOF–OCH 3 . In the flow cell, the ECO 2 R evaluation results of Cu-SOF–OCH 3 showed that the Faradaic efficiency of CH 4 reached 65.9% at −1.2 V, which was superior to the similar catalysts reported in literatures. Further theoretical calculations showed that the HOMO-LUMO gap of Cu-SOF–OCH 3 was lower than that of Cu-SOF-H, which accelerated the electron transfer between the Cu site and the CO 2 molecule. Notably, Cu-SOF–OCH 3 exhibited a lower energy barrier in the process of generating *COOH and *CHO than Cu-SOF without the –OCH 3 group, which promoted the CH 4 formation.
研究领域:
材料科学
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电催化
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Yuqi Zhang,Jiasi Yan,Rixin You,Meng He,Ligen Wang,Minghui Liang
The catalytic epichlorohydrin (ECH) hydrogenation to chloro-propanol is of great industrial importance due to the extensive application of chloro-propanol as an intermediate for pharmaceutics, fine chemicals, and polymers. The challenge of this catalytic reaction lies in that dechlorination can hardly be inhibited in the selective hydrogenation of the epoxy group because the bond energy of the C-Cl bond is very close to that of the C O bond. Herein, we demonstrated that the selectivity of chloro-propanol could be improved from 82.2 % to 94.6 % by incorporating a small amount of Cu single atoms into Pt/C catalysts to inhibit dechlorination. More interestingly, the ring-opening site of the epoxy group can be also engineered by the incorporation of Cu single atoms, as evidenced by the significant increase in the selectivity of 3-chloro-1-propanol from 0.2 % to 14.5 %. Comprehensive characterizations and density functional theory (DFT) calculations were carried out to understand the interplay of Cu single atoms and Pt nanoparticles as well as its effect on the catalytic performance. The insights gained in this study will benefit the development of catalysts, especially the bimetallic catalysts for the selective hydrogenation of halogeno-aliphatic compounds.
研究领域:
催化
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化学工程
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材料科学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2023
·Vol. 120
·期 43
·e2311585120
·
IF 11.1
Chao-Hai Gu,Song Wang,Ai-Yong Zhang,Chang Liu,Jun Jiang,Han-Qing Yu
Single-atom Fenton-like catalysis has attracted significant attention, yet the quest for controllable synthesis of single-atom catalysts (SACs) with modulation of electron configuration is driven by the current disadvantages of poor activity, low selectivity, narrow pH range, and ambiguous structure–performance relationship. Herein, we devised an innovative strategy, the slow-release synthesis, to fabricate superior Cu SACs by facilitating the dynamic equilibrium between metal precursor supply and anchoring site formation. In this strategy, the dynamics of anchoring site formation, metal precursor release, and their binding reaction kinetics were regulated. Bolstered by harmoniously aligned dynamics, the selective and specific monatomic binding reactions were ensured to refine controllable SACs synthesis with well-defined structure–reactivity relationship. A copious quantity of monatomic dispersed metal became deposited on the C3N4/montmorillonite (MMT) interface and surface with accessible exposure due to the convenient mass transfer within ordered MMT. The slow-release effect facilitated the generation of targeted high-quality sites by equilibrating the supply and demand of the metal precursor and anchoring site and improved the utilization ratio of metal precursors. An excellent Fenton-like reactivity for contaminant degradation was achieved by the Cu1/C3N4/MMT with diminished toxic Cu liberation. Also, the selective ·OH-mediated reaction mechanism was elucidated. Our findings provide a strategy for regulating the intractable anchoring events and optimizing the microenvironment of the monatomic metal center to synthesize superior SACs.
研究领域:
催化
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环境科学
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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
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Cui Zhang,Saiyu Dong,Zhaoli Liu,Nairu Liu,Xi Zhang,Jie Dong,Xueping Zhou,Yirong Guo,Jianxiang Wu
Immunochromatographic test strip (ITS) has been widely employed for point-of-care diagnoses. However, how to significantly enhance the analytical sensitivity of device-free ITS remains a challenge. Here, we synthesized a Cu single-atom anchored Co 3 O 4 (CuSA/Co 3 O 4 ) nanozyme that possesses ultrahigh peroxidase-mimicking catalytic activity owing to d -band center upshift mediated by Cu single-atom. Molecular orbital analysis demonstrated that d orbitals in CuSA/Co 3 O 4 have stronger orbital hybridization affinity than Co 3 O 4 to H 2 O 2 ′s π* orbitals. This reinforces hydroxyl radical ( OH) production and provides a stronger catalytic colorimetric signal, which is beneficial for improving the sensitivity of ITS. Moreover, we applied the CuSA/Co 3 O 4 to ITS as a signal reporter for monitoring Xanthomonas oryzae pv. oryzicola (Xoc) , the pathogen of rice bacterial leaf streak. The visual limit of detection (LOD) of the developed CuSA/Co 3 O 4 -based ITS was as low as 6.4 × 10 2 CFU mL −1 , which is 25-fold more sensitive than the traditional Au nanoparticles (AuNP)-based ITS. Taken together, this work demonstrates the great potential of CuSA/Co 3 O 4 nanocomposite as a signal reporter to improve the sensitivity of ITS for on-site Xoc detection.
研究领域:
分析化学
·
纳米技术
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生物技术
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植物病理学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Mao Qiqi,Mu Xu,Wang Wenxin,Deng Kai,Yu Hongjie,Wang Ziqiang,Xu You,Wang Liang,Wang Hongjing
Organic electrocatalytic conversion is an essential pathway for the green conversion of low-cost organic compounds to high-value chemicals, which urgently demands the development of efficient electrocatalysts. Here, we report a Cu single-atom dispersed Rh metallene arrays on Cu foam for cathodic nitrobenzene electroreduction reaction and anodic methanol oxidation reaction. In the coupled electrocatalytic system, the Cu single-atom -Rh metallene arrays on Cu foam requires only the low voltages of 1.18 V to reach current densities of 100 mA cm −2 for generating aniline and formate, with up to ~100% of nitrobenzene conversion/ aniline selectivity and over ~90% of formate Faraday efficiency, achieving synthesis of high-value chemicals. Density functional theory calculations reveal the electron effect between Cu single-atom and Rh host and catalytic reaction mechanism. The synergistic catalytic effect and H*-spillover effect can improve catalytic reaction process and reduce energy barrier for reaction process, thus enhancing electrocatalytic reaction activity and target product selectivity.
研究领域:
化学工程
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电化学
·
催化
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材料科学
✓ 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）