Nanoscale
·
2024
·Vol. 16
·期 28
·13642-13653
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IF 5.8
Ziyin Yang,Chongchao Zhang,Chengcheng Qi
Which is more suitable as a sensing material between metal single-atoms and nanoparticles? Herein, electrocatalytic behaviors of copper single-atoms (Cu SAs) and copper nanoparticles (CuNPs) toward H2O2 reduction and glucose oxidation were studied. Surprisingly, the electrocatalytic activity of Cu SAs and CuNPs showed significant differences in H2O2 reduction and glucose oxidation. Compared with CuNPs, Cu SAs exhibit outstanding activity in the electrocatalytic reduction of H2O2 but exhibit weak activity in the electrocatalytic oxidation of glucose. On the contrary, CuNPs exhibit excellent activity in the electrochemical oxidation of glucose but have very weak electrocatalytic activity towards H2O2 reduction. DFT results show that H2O2 reduction is more favourable with Cu SAs; however, the electrochemical oxidation of glucose with CuNPs requires overcoming much lower energy barriers than that with Cu SAs. This study proves that both metal single-atoms and nanoparticles are not omnipotent, which provides ideas for constructing highly active sensing materials.
研究领域:
材料科学
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电化学
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生物传感
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2020
·
IF 10.652
Huiyuan Cheng,Xuemei Wu,Xiangcun Li,Xiaowa Nie,Shuai Fan,Manman Feng,Zihao Fan,Mingqian Tan,Yonggang Chen,Gaohong He
Although considerable progress has been achieved by Cu nanoparticles for catalyzing CO 2 reduction reaction (CO2RR), Cu single atom catalysts (Cu SACs) are generally suffered from inferior performance to that of widely investigated Fe, Co, Ni SACs. This phenomenon mainly ascribes to the lack of effective geometry and electronic engineering of copper active center from an atomic level. Herein, highly exposed atomically dispersed Cu-N x ( x denotes Cu–N coordination number) sites anchored on 3D porous carbon matrix are successfully synthesized through facile one step thermal activation, and Cu-N 4 sites exhibit boosted activity and selectivity compared to its nearly inert Cu-N 3 counterparts. Aided by density functional theory (DFT) calculations, the edge-hosted Cu-N 4 moieties are revealed as key active sites for efficient CO generation via optimized local coordination environment and electronic properties, which strongly interact with *COOH intermediate and facilitate the desorption of *CO. As a result, Cu-N 4 catalyst achieves high CO Faradaic efficiency (FE CO ) of over 90% from −0.6 to −1.1 V vs . RHE with a maximum value of 98%, surpassing the previously reported Cu SACs for CO 2 -to-CO conversion. This work provides new insight into proper Cu SACs design and fundamental mechanism understanding to boost CO2RR.
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
Advanced Energy Materials
·
2023
·Vol. 13
·期 42
·2302692
·
IF 27.8
Qingyu Wang,Yida Zhang,Minxi Lin,Hengwei Wang,Yu Bai,Chengyuan Liu,Junling Lu,Qiquan Luo,Gongming Wang,Hai-Long Jiang,Tao Yao,Xusheng Zheng
Metastable structures are promising candidates for efficient catalysis owing to abundant active electronic states, strong electronic coupling with reactants, and energetic preference. Exerting the value of metastable structures while evading the difficulty in direct synthesis remains challenging. Herein, it is reported that light irradiation enables the generation and maintenance of the metastable state over copper single atoms for efficient carbon dioxide reduction. Under irradiation with light, photogenerated electrons transit to Cu-3 d orbits and initiate d -orbital rearrangement. The initial symmetric Cu 1 ─O 4 coordination converts to the metastable asymmetric structure of Cu 1 ─O 2+1 , and is reversibly restored after removing the light. The photoinduced metastable intermediate of Cu 1 ─O 2+1 promotes the Cu single-atom catalyst to deliver an ethylene yield rate of 60.4 µmol g cat. −1 h −1 . Mechanistic studies reveal that Cu 1 ─O 2+1 possesses stronger adsorption capability for reactants and intermediates. The reaction energy barrier over Cu 1 ─O 2+1 also shows an obvious decline compared to that over Cu 1 ─O 4 .
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
RARE METALS
·
2024
·
IF 9.6
Feng Yu-Xiao,Yu Hui-Jun,Lu Tian-Guang,Zheng Zi-Ye,Tian Shuang,Xiang Li,Zhao Shan,Wang Shu-Guang,He Zuo-Li
Metal clusters or even single-atoms dispersed and anchored on the photocatalysts’ surface can enhance photocatalytic performances on organic pollutant oxidation. Here, a simple photoreduction method was used to create atomically dispersed metal single-atoms/clusters (MSCs, M = Cu, Pd, Au and Ag) on P-modulated tubular carbon nitride (TCN). The obtained MSCs@TCN demonstrated excellent photocatalytic performances for the degradation of sulfamethazine (SMZ). In particular, the photocatalyst with 2 wt% Cu loading showed ultrahigh SMZ oxidation efficiency ( k = 0.06110 min −1 ), almost three times that of TCN ( k = 0.02066 min −1 ). It also shows excellent stability in the 5th-cycle measurements. The improved photocatalytic activity of the CuSCs@TCN is ascribed to the synergistic promotion of photogenerated charge separation by Cu single-atoms/clusters as active sites, accelerated charge transfer from bulk TCN to Cu sites through Cu–N x interaction. Meanwhile, the active sites of Cu single-atoms/clusters could promote the production of ·O 2 − , which participates in organic oxidation with strong oxidizing holes (h + ). This strategy paves a new avenue for designing high-performance photocatalysts decorated with metal single-atoms and clusters.
研究领域:
材料科学
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环境科学
·
化学
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产品关联
DOI
高影响因子
ACS Applied Nano Materials
·
2021
·
IF 5.097
Yang Liu,Wei Guo,Xiaojun Li,Peng Jiang,Ning Zhang,Minghui Liang
The selective hydrogenation of alkynes to alkenes is very important for both industry and scientific investigation, and overhydrogenation of alkynes to alkanes is the biggest problem to be solved. Suppressing the catalytic hydrogenation of alkenes to alkanes and keeping the efficient conversion from alkynes to alkenes at the same time is a viable solution, but the slight difference in structure between alkynes and the corresponding alkenes causes great difficulty in realizing such a target. The Pt/C–Cu bimetallic catalysts are used to catalyze the selective hydrogenation of phenylacetylene (PA) to styrene (ST). High-resolution STEM and EXAFS results show that the prepared Pt/C–Cu catalysts are composed of copper single atoms and Pt nanoparticles. In particular, Pt/C–Cu is a catalyst in which copper single atoms cover the surface of Pt nanoparticles. The experimental results reveal that the selectivity of ST strongly depends on the coverage of Cu single atoms over Pt nanoparticles in Pt/C–Cu, so selective hydrogenation of PA is a structure-sensitive reaction. The selectivity of ST can reach 94.4% at a PA conversion of 100% in the selective hydrogenation of PA over Pt/C–0.5Cu, an optimized Pt–Cu bimetallic catalyst; after selective removal of PA in ST from 100 to 30 ppm over the same catalyst, the yield of ST reaches 99.97%. The chemisorption results of H2 and probe molecule ethene (C2H4) over the Pt–Cu/C catalysts reveal that Cu single atoms covering on the surface of Pt nanoparticles weaken the Pt–H and Pt–C2H4 interactions, so the catalytic hydrogenation of the carbon–carbon double bond over Pt/C–0.5Cu can be tremendously suppressed. The added Cu single atoms over Pt nanoparticles are not poisonous sites because they can also act as the active centers to activate hydrogen and the carbon–carbon double bond.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
RSC Advances
·
2023
·Vol. 13
·期 13
·8915-8922
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IF 3.9
Tong Zhou,Haitang Wei,Bin Xiao,Tianping Lv,Liangfei Duan,Qingjie Lu,Jin Zhang,Yumin Zhang,Qingju Liu
One of the most promising strategies for producing hydrogen is photocatalytic water splitting, in which the photocatalyst is a key component. Among many semiconductor photocatalysts, g-C3N4 has attracted great attention due to its narrow band gap, excellent stability and low cost. However, practical application is limited by its poor intrinsic activity. In this work, a high-performance porous g-C3N4 (PCN) photocatalyst with anchored Cu single atoms (CuSAs) was synthesized by a one-step co-heating approach. The obtained Cu1.5–PCN displays an excellent hydrogen evolution rate (HER) of 2142.4 μmol h−1 g−1 under visible light (=420 nm), which is around 15 and 109 times higher than those of PCN and bulk g-C3N4, respectively. In addition, it also shows good stability during H2 evolution. The results of experimental research and DFT simulations indicate that the single Cu ions formed bonds with the N-ring and these remain stable. Meanwhile, the special electronic structure of the Cu–N charge bridge extends the light absorption band to the visible-light region (380–700 nm). This high-performance and low-cost photocatalyst has great potential in solar energy conversion.
研究领域:
材料科学
·
能源化学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Yan Liu,Yamin Zheng,Panpan Dong,Wenzhuang Zhang,Wenjie Wu,Junjie Mao
Development of high-performance heterogeneous catalytic materials is important for the rapid upgrade of chemicals, which remains a challenge. Here, the benzene oxidation reaction was used to demonstrate the effectiveness of the atomic interface strategy to improve catalytic performance. The developed B,N-cocoordinated Cu single atoms anchored on carbon nanosheets (Cu1/B–N) with the Cu–N2B1 atomic interface was prepared by the pyrolysis of a precoordinated Cu precursor. Benefiting from the unique atomic Cu–N2B1 interfacial structure, the designed Cu1/B–N exhibited considerable activity in the oxidation of benzene, which was much higher than Cu1/N–C, Cu NPs/N–C, and N–C catalysts. A theoretical study showed that the enhanced catalytic performance resulted from the optimized adsorption of intermediates, which originated from the manipulation of the electronic structure of Cu single atoms induced by B atom coordination in the Cu–N2B1 atomic interface. This study provides an innovative approach for the rational design of high-performance heterogeneous catalytic materials at the atomic level.
研究领域:
材料科学
·
催化化学
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DOI
高影响因子
RARE METALS
·
2025
·
IF 11
Wu Jing,Rong Jian,Chen Wang-Yi,Wang Chao-Sheng,Feng Chu-Jun,Ao Huai-Sheng,Zhu Cheng-Zhang,Zhang Yu-Zhe,Li Zhong-Yu
Regulating the electronic structure and oxygen-containing intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction (ORR) kinetics, but it still remains a great challenge. In this work, Fe atom clusters (Fe AC ) modified by high-density Cu single atoms (Cu SA ) in a N,S-doped porous carbon substrate (Fe AC /Cu SA @NCS) is reported for enhanced ORR electrocatalysis. Fe AC /Cu SA @NCS exhibits excellent ORR performance with a half-wave potential ( E 1/2 ) of 0.911 V, a high four-electron process selectivity and excellent stability. The ORR performance is also verified in the Fe AC /Cu SA @NCS-based Zn-air battery, which shows a high peak power density of 192.67 mW cm −2 , a higher specific capacity of 808.3 mAh g −1 and impressive charge–discharge cycle stability. Moreover, density functional theory calculations show that Cu single atoms synergistically modulate the electronic structure Fe active atoms in Fe atomic clusters, reducing the energy barrier of the rate-determining step (i.e., * OH desorption) on Fe AC /Cu SA @NCS. This work provides an effective way to regulate the electronic structure of Fe-based catalysts and optimize their electrocatalytic activity based on the introduction of a second metal source. Graphical abstract
研究领域:
材料科学
·
电化学
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产品关联
DOI
高影响因子
ACS Applied Nano Materials
·
2024
·
IF 5.3
Xiangwei Yuan,Yao Jin,Junchun Guo,Qain Wang,Li Xu,Yongjiao Song,Xiaoli Xiong
N-doped hollow carbon spheres loaded with Cu single atoms (Cu SAs/N-CSs) were prepared via an in situ hard-template method. As an electrode catalyst, the Cu SAs/N-CSs electrochemical-sensing properties to hydroquinone (HQ) and catechol (CC) were investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), and the linear detection ranges of HQ and CC were 1–324 and 1–123 μM, respectively; the detection limits are 0.33 and 0.17 μM, respectively. The experimental and DFT calculation results show that Cu SAs/N-CSs have stronger adsorption strength and more effective affinity for CC and HQ due to the synergistic effect of dispersed Cu SAs and N-CSs, thus improving the electrocatalytic and sensing properties of CC and HQ. Furthermore, the prepared electrode has been successfully applied to the simultaneous determination of HQ and CC in practical water samples with satisfactory results.
研究领域:
材料科学
·
分析化学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Zhipeng Guo,Wei Wei,Yihang Li,Xianghong Niu,Fengming Hou,Jin Li,Xiaoke Zhang,Xiuyun Zhang,Ang Wei
Single-atom photo-Fenton (PF) reaction is widely employed for the degradation of antibiotics and water disinfection. However, the key fundamental issues of the valence state cycling of single-atom metals and the activation of hydrogen peroxide (H 2 O 2 ) in the PF process remain indistinct. Herein, we developed a catalyst donated as Cu single atoms anchored hydrangea-like carbon nitride (Cu-SA/CNH) with Cu−N 4 coordination for PF reaction. Compared to pristine CNH, the Cu-SA/CNH exhibited a 2.42-fold increase in PF kinetics. The Cu-SA/CNH/PF system achieved 98.1% degradation efficiency of tetracycline and effectively inactivated Escherichia coli within 30 min. Density functional theory calculations demonstrated that the formation of Cu−N 4 effectively improved the energy of the Cu d orbitals, leading to the generation of intermediate states that facilitated the Cu 2+ /Cu + cycle. The adsorption capacity of Cu d xz orbitals on H 2 O 2 increased nearly 10 times. This work provides valuable insights for enhancing single-atom PF activity to address environmental pollution.
研究领域:
环境科学
·
材料科学
·
理论化学
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Mingyue Xie,Yong Wu,Hao Gu,Yuhao Peng,Shan Zhang,Feng Ryan Wang,Wei Xiao,Dong Gu
Deuterated compounds have broad applications across various fields, with dehalogenative deuteration serving as an efficient method to obtain these molecules. However, the diverse electronic structures of active sites in the heterogeneous system and the limited recyclability in the homogeneous system significantly hinder the advancement of dehalogenative deuteration. In this study, we present a catalyst composed of copper single-atom sites anchored within an ordered mesoporous nitrogen-doped carbon matrix, synthesized via a mesopore confinement method. The Cu1/OMNC-1100 catalyst, characterized by Cu–N4 sites, demonstrates exceptional performance, high functional group tolerance, and remarkable durability in the deuteration of 2-bromo-6-methoxynaphthalene under relatively mild conditions (80 °C, 2 MPa of CO). Experimental results combined with X-ray absorption fine structure analysis reveal that Cu–N3 sites can be converted into more stable Cu–N4 counterparts at higher pyrolysis temperatures, resulting in enhanced catalytic activity. This work demonstrates a strategy for designing single-atom site catalysts with tunable coordination environments, providing a promising approach to improving catalytic performance in selective dehalogenative reactions under relatively mild conditions.
研究领域:
化学
·
材料科学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2023
·
IF 5.9
Zhaolei Ma,Ruoning Bai,Wei Yu,Guoxian Li,Chuizhou Meng
Transition metal single atoms have been considered as promising candidates for oxygen reduction reaction catalysts for developing high-performance zinc–air batteries. How to uniformly disperse metal single atoms onto an ideal porous carbon framework for full utilization of the catalyst with enriched active sites and fast mass diffusion still remains a challenge. Herein, by taking advantage of both the efficient single-atom Cu catalyst and the effective NaCl-template sacrificing method, we report the design and fabrication of a single-atom Cu catalyst decorated on a three-dimensional (3D) nitrogen–carbon (NC) framework. The developed catalyst exhibits excellent (oxygen reduction reaction) ORR catalytic activity with a high half-wave potential of 0.86 V, maximum current density of 5.53 mA cm–2, and Tafel slope of 81.52 mV dec–1, which are better than those of the commercial Pt/C catalyst. The comparison experiment with the 3D NC framework (no copper salt added) and the bulk Cu decorated NC framework (no NaCl added) verifies the synergistic effect between the Cu single atoms as the efficient ORR catalyst and the NaCl template to achieve the ideal porous structure. Aqueous zinc–air batteries assembled with the developed catalyst deliver good battery performance with a high open circuit voltage of 1.48 V, large specific discharge capacity of 760.47 mAh g–1, high peak power density of 120 mW cm–2, and stable charge–discharge cyclability for 600 h. Gel polymer electrolyte-based zinc–air batteries are also demonstrated to be workable under bending conditions for practical wearable electronic applications.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）