Catalysts
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2023
·Vol. 13
·期 4
·776
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IF 3.9
Xing Shen,Kairui Liu
Single-atom catalysts (SACs) have been synthesized using a variety of methods in recent years, and they have shown excellent catalytic activities. However, metal atoms show a high tendency to agglomerate in liquid media, making the single atom synthesis more difficult in liquid media. The synthesis of such metal single-atom catalysts that do not have strong ligand coordination is rarely reported in the literature. Herein, we report the facile synthesis of monodispersed Au atoms (Au1) through the reduction in HAuCl4in 15-crown-5. The complete reduction in HAuCl4was confirmed through UV-Vis spectroscopy. In addition, the Au was found in a zero valence state after reduction, which was confirmed through XPS and XANES results. Moreover, the dispersion of Au was confirmed as a single atom (Au1) through transmission electron microscopy and spherical aberration electron microscopy. The possible structure of this catalyst was proposed by matching the EXAFS results with the structure of Au1@15-crown-5 as -(OC2H4O)-AuCl2H2. The Au1@15-crown-5 showed high activity (TOF as high as 22,075) in the reduction in nitrophenol and nitroaniline to aminophenol and phenylenediamine by sodium borohydride. Because of the monodispersion of Au atoms, its performance is much better than noble nanoparticles and non-precious metal catalysts.Keywords:gold;single atom;nitroaromatic compounds reduction;catalysis
研究领域:
化学
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材料科学
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DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2025
·
IF 2.5
Ziru Shao,Shuangfei Zhang,Deyong Wu
Single-atom catalysts (SACs) have been increasingly investigated in Fenton-like reactions for emerging pollutants degradation. Herein, single atom Cu anchored on porous polymeric carbon nitride (SA-Cu/PCN-α) was prepared for peroxymonosulfate (PMS) activation on tetracycline (TC) removal. The as-prepared composites were comprehensively characterized by SEM, TEM, XRD, XPS, and EDS, confirming the successful incorporation of Cu single atoms and the formation of a porous heterostructure. SA-Cu/PCN-α efficiently activated peroxymonosulfate (PMS) to degrade TC, with a pseudo-first-order rate constant k of 0.843 min⁻¹-18.7-fold higher than that of pure PCN (0.045 min⁻¹). Mechanistic studies revealed that Cu single atoms modulated the electronic structure of PCN, promoting charge separation and generating abundant reactive oxygen species (ROS, primarily 1 O 2 and O 2 •-). Static experiments indicated that the degradation efficiency remained above 80% under wide ranges of pH (3-11) and PMS dosage (0.5-2.0 mM) within 10 min. The catalyst retained 80% activity after five cycles, demonstrating its stability.Overall, this work designs Cu SACs with promising implications for wastewater treatment.
研究领域:
环境科学
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催化
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材料科学
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化学工程
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水处理
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DOI
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-11
·
IF 17.694
Zhao Xin,Fang Ruiqi,Wang Fengliang,Kong Xiangpeng,Li Yingwei
Single-atom (SA) catalysts provide extensive possibilities in pursuing fantastic catalytic performances, while their preparation still suffers from metal aggregation and pore collapsing during pyrolysis. Here we report a versatile medium-induced infiltration deposition strategy for the fabrication of SAs and hetero-SAs (M a N 4 /M b N 4 @NC; M a = Cu, Co, Ni, Mn, M b = Co, Cu, Fe, NC = N-doped carbon). In-situ and control experiments reveal that the catalyst fabrication relies on the “step-by-step” evolution of M a -containing metal-organic framework (MOF) template and M b -based metal precursor, during which molten salt acts as both pore generator in the MOF transformation, and carrier for the oriented infiltration and deposition of the latter to eventually yield metal SAs embedded on hierarchically porous support. The as-prepared hetero-SAs show excellent catalytic performances in the general synthesis of 33 kinds of natural flavones. The highly efficient synthesis is further strengthened by the reliable durability of the catalyst loaded in a flow reactor. Systematic characterizations and mechanism studies suggest that the superior catalytic performances of CuN 4 /CoN 4 @NC are attributed to the facilitated O 2 activating-splitting process and significantly reduced reaction energy barriers over CoN 4 due to the synergetic interactions of the adjacent CuN 4 .
研究领域:
催化
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材料科学
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化学工程
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有机合成
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DOI
PubMed
高影响因子
PROCEEDINGS OF THE COMBUSTION INSTITUTE
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2022
·
IF 6.535
Xing Yuan,Chaohe Zheng,Zuwei Xu,Qinghua Yang,Tiantian Zhang,Xi Luo,Haibo Zhao
Photothermocatalytic oxidation is an environmentally-friendly, low-temperature, and high-efficient method to remove the air pollutant. Yet, the lack of active, inexpensive, and superior stability catalysts has greatly limited its extensive utilization. In this work, the effect of single-atom Pt loading on TiO 2 support has been theoretically and experimentally studied to improve photothermocatalytic performance for the toluene combustion through flame spray pyrolysis (FSP). Pt loading can play two crucial roles into TiO 2 optimization: (1) The low-valence Pt cation incorporated into TiO 2 lattice is dramatically responsible for the anatase-rutile transformation (ART) and formation of sufficient oxygen vacancies ; (2) Introducing the defect energy level and Pt-3d orbitals remarkably promote the charge separation efficiency of single-atom catalysts. Moreover, the existence of single-atom Pt nanoparticles can signally boost the activity of surface adsorbed and lattice oxygen, as well as substantially reduce the oxygen vacancy formation energy. Thus, the toluene removal under light irradiation reaches 90% conversion below 160 °C and is maximally 18 °C lower than that under only thermocatalytic oxidation. It is attributed to larger specific surface area (SSA), outstanding low-temperature reducibility, extremely dispersed hybrid PtO x , more surface active oxygen, and higher mobility of bulk oxygen. Interestingly, when the oxygen-fuel equivalent ratio φ distinctly increases by shifting precursor solvent from xylene to ethanol, the photothermocatalytic property of toluene can be remarkably enhanced on single-atom Pt catalysts. It is due to the higher Pt dispersion resulting from more intense burning and drastic turbulent mixing, as well as the superior ratio of the metallic Pt active sites originating from higher flame temperature. Eventually, the rate-determining step of C 7 H 8 combustion on Pt/TiO 2 and Cu/TiO 2 slab are all the C C bond fracture of maleic anhydride to form acetic anhydride species, with the energy barriers of 112.03 and 188.74 kJ/mol, respectively.
研究领域:
环境科学
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催化化学
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2024
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IF 8.1
Xin Sun,Jun Wang,Jing Yu,Yifu Jing,Jingyuan Liu,Manish Singh,Peter D. Lund,Muhammad Imran Asghar
Atomic isolated and dispersed single atom catalyst is ideal for high-performance industrial catalyst. However, the contribution from small amounts of nanoclusters coexisting with single atoms to the catalytic reaction activity is often neglected. In this work, a MXene-supported uniformly dispersed Pt single atoms and nanoclusters (Pt 1 +Pt n /MXene) were obtained by self-assembly through an impregnation method. The catalyst exhibits high electrochemical performance in the hydrogen evolution reaction with an overpotential of only 61.3 mV and a Tafel slope of 32.5 mV dec −1 at a current density of 10 mA cm −2 in an acidic environment. The XAFS analysis and further DFT calculation indicate that the synergistic effect between single atoms and nanoclusters can facilitate adsorption of H* and promote the HER reaction. This work provides an efficient method for integrating multiple active sites in noble metal catalysts.
研究领域:
材料科学
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催化化学
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能源科学
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DOI
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Mufan Wang,Shiying Fan,Xinyong Li,Jugong Shi,Yan Mao,Yaqi Yang,Gao Li
Efficiently upgrading 5-hydroxymethylfurfural (HMF) into high-value-added products, such as 2,5-diformylfuran (DFF) and 2,5-furan dicarboxylic acid (FDCA), through a photocatalytic process by using solar energy has been incessantly pursued worldwide. Herein, a series of transition-metal (TM = Ni, Fe, Co, Cu) single atoms were supported on Ti4+αTi3+1-αO2−δ nanofibers (NFs) with certain defects (Ov), denoted as TM SAC-Ti4+αTi3+1-αO2−δ NFs (TM = Ni, Fe, Co, Cu), aiming to enhance the photocatalytic conversion of HMF. A super HMF conversion rate of 57% and a total yield of 1718.66 μmol g–1 h–1 (DFF and FDCA) surpassing that of the Ti4+αTi3+1-αO2−δ NFs by 1.6 and 2.1 times, respectively, are realized when TM is Co (Co SAC-Ti4+αTi3+1-αO2−δ NFs). Experiments combined with density functional theory calculation (DFT) demonstrate that the TM single atoms occupy the Ti site of Ti4+αTi3+1-αO2−δ NFs, which plays a dominant role in the photo-oxidation of HMF. Raman, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) characterizations confirm the strong electron local exchange interaction in TM SAC-Ti4+αTi3+1-αO2−δ NFs and demonstrate the substitution of Ti by the TM SACs. The projected density of states and charge density difference reveal that the strong interaction between metal-3d and O-2p orbitals forms Ti–O–TM bonds. The bonds are identified as the adsorption site, where TM single atoms on the surface of Ti4+αTi3+1-αO2−δ NFs reduce HMF molecule adsorption energy (Eads). Furthermore, the TM single atom modulates the electronic structure of TM SAC-Ti4+αTi3+1-αO2−δ NFs through electron transfer, leading to narrow band gaps of the photocatalysts and enhancing their photocatalytic performance. This study has uncovered a newer strategy for enhancing the photocatalytic attributes of semiconducting materials.
研究领域:
材料科学
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化学工程
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环境科学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
·
IF 13.2
Chengcheng Qi,Yaqi Kong,Ziyin Yang
The regulation of the activity of single-atom nanozymes is crucial for the development of highly sensitive electrochemical sensors. The accessibility of single-atom nanozymes is an important factor limiting their activity. This study proposes a directional anchoring strategy to regulate the accessibility of single-atom nanozymes for boosting electrochemical nonenzymatic H 2 O 2 sensing. The directional anchoring of Fe single-atoms on the inner surface of nitrogen-doped carbon materials (In-Fe SAs/NC) and the outer surface of nitrogen-doped carbon materials (Out-Fe SAs/NC) was achieved via the hard template assisted method. The impact of the anchoring position of Fe SAs on the electrocatalytic reduction of H 2 O 2 was investigated. Density functional theory (DFT) calculations reveal that Fe SAs nanozymes are more likely to activate H 2 O 2 than the previously reported Fe 3 O 4 nanozymes. The anchoring of Fe SAs on the outer surface of NCs markedly enhances the accessibility of active sites in comparison to anchoring Fe SAs on the inner surface, thereby increasing the sensitivity for the detection of H 2 O 2 . The electrochemical sensor based on Out-Fe SAs/NC can be used to detect H 2 O 2 content in milk samples. The high accessibility and excellent intrinsic activity of Fe SAs render Out-Fe SAs/NC a highly effective sensing material.
研究领域:
材料科学
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分析化学
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生物医学工程
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DOI
高影响因子
ACS Applied Nano Materials
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2024
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IF 5.3
Xihui Lu,Jinshan Wei,Hexing Lin,Yi Li,Ya-yun Li
Electrocatalytic reduction of nitrate (NO3RR) to ammonia offers a promising approach for mitigating the environmental impact of NO3–, while simultaneously enabling the synthesis of NH3 under ambient conditions. Recently, single-atom catalysts (SACs) have been proven to have attractive activity on NO3RR, and better catalysts with enhanced activity and stability are still in demand. Here, we report the efficient boosting of NH3 production via the NO3RR using boron-doped Fe SAC (Fe-BCN). Fe-BCN is a normal 12-hedral nanoparticle with a size of 500 nm. The NH3 Faradaic efficiency of Fe-BCN reached 97.48%, with a high ammonia production rate of 2.17 mg cm–2 h–1, in an alkaline electrolyte environment at an electrode potential of −0.3 V vs reversible hydrogen electrode. Density functional theory calculations revealed the strategy of introduced B regulating the intermediate adsorption on Fe-BCN, which enhanced the NO3RR activity. Furthermore, leveraging the high NO3RR activity of Fe-BCN, a nitrate-zinc battery with a power density of 0.90 mW cm–2 was constructed by using Fe-BCN as the cathode and zinc as the anode, respectively. This research demonstrates the broad prospects of Fe-BCN in the NO3RR and provides insights for high-performance Fe SAC electrode materials.
研究领域:
催化化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
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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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Xiangyu Jia,Kai Yuan,Guofu Wang,Shanhui Zhu,Mei Dong,Jiamin Wang,Xiaoming Li,Weibin Fan
Selective reduction of 5-hydroxymethylfurfural (HMF) to valuable 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) remains a significant challenge under mild conditions. The synergistic effect between metal single atoms (SAs) and nanoparticles (NPs) can greatly enhance catalytic activity. Here, a high-performance Pd SAs catalyst supported on N-doped carbon (PdSAs/NC) was developed from Pd@UiO-66-NH 2 . It was found that partial Pd SAs were spontaneously restructured into Pd NPs during the reaction. Our catalyst exhibited 100 % conversion of HMF and 98 % selectivity towards BHMTHF at temperature as low as 0 °C. In situ FTIR spectra results and density functional theory calculations indicate that Pd SAs contribute to the C = O activation, while Pd NPs facilitated the H 2 dissociation into H* atoms, resulting in synergistic catalytic activity between Pd SAs and Pd NPs.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
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IF 7.2
Yang Xiao,Chao Qu,Jingjing Zhang,Xi Chen,Wenjin Wang,Xuelong Zheng,Qing Ye
The dissociation of water is essential to water gas shift (WGS) reaction, and the presence of oxygen vacancies can facilitate this key step. Herein, a series of perovskite supported Pd single atoms catalysts were prepared via deposition precipitation method. The incorporation of Pd single atoms can effectively promote the formation of oxygen vacancy on the surface of the catalyst, improving the low temperature reducibility, the ratio of Mn 4 + /Mn 3+ and O ads /O lat compared with support. Among all samples, 0.82 Pd/La 0.5 Ca 0.5 MnO 3 /SBA-15 with the most oxygen vacancies presented 83.6 % CO conversion at 400 °C, specific reaction rate (0.54 mol CO g Pd −1 h −1 ), and TOF (3.77✕10 −2 s −1 ). DFT calculation proved that Pd doping can effectively decreased energy barrier of H 2 O dissociation, and promoted the formation of oxygen vacancies. This work provides experimental and theoretical insights into the rational design of highly active perovskite supported Pd single atom catalysts for WGS reaction.
研究领域:
催化化学
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材料科学
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理论计算
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DOI
高影响因子
ChemCatChem
·
2021
·Vol. 13
·期 7
·1834-1846
·
IF 5.686
Ruihuan Jiang,Shaomian Liu,Liang Li,Yongjun Ji,Huifang Li,Xiangfeng Guo,Lihua Jia,Ziyi Zhong,Fabing Su
Graphical Single Ir atoms : In the CO+NO reaction, the catalyst with single-sited Ir atoms (0.28 wt %) anchored on a mesoporous WO 3 (Ir 1 /mesoporous-WO 3 ) showed much higher NO conversion and N 2 selectivity under oxygen-rich conditions than the catalysts supported with Ir nanoparticles on the same catalyst support (Ir NPs/mesoporous-WO 3 ) and on a non-mesoporous WO 3 (Ir/non-mesoporous-WO 3 ). Under oxygen-rich conditions, achieving a selective and efficient reduction of NO by CO is always challenging. Here, we report the synthesis of the catalyst consisting of single Ir atoms anchored on mesoporous WO 3 (denoted as Ir 1 /m-WO 3 ) using a facile template method followed by wet impregnation. X-ray diffraction and transmission electron microscope studies indicated that the Ir atoms were distributed uniformly on the internal surface of m-WO 3 . When tested for the reduction of NO by CO, the Ir 1 /m-WO 3 catalyst with a low Ir loading of 0.28 wt % exhibited excellent catalytic performance in the presence of 2 vol % O 2 (volume ratio of CO to O 2 being 1 : 10), achieving a NO conversion of 73 % and N 2 selectivity of 100 % at 350 °C. In particular, its turnover frequency (TOF) value reached 0.30 s −1 at 200 °C, which is six times higher than that of the catalyst with Ir nanoparticles supported on mesoporous WO 3 (0.05 s −1 ). The superior catalytic performance of Ir 1 /m-WO 3 is attributed to the formation of the isolated Ir atoms and the more newly generated Ir-WO 3 interfaces that can promote the adsorption and activation of NO, and the presence of accessible mesopores in m-WO 3 that facilitates the mass transfer of NO and CO. This study brings a new fundamental understanding of active sites in Ir-based catalysts for the CO+NO reaction and provides a new way to the design and synthesis of single-atom catalysts, especially precious metal catalysts for emissions control.
研究领域:
催化化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
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