ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Yan Gu,Tiefeng Xu,Zhexin Zhu,Xiufang Chen,Wenxing Chen,Wangyang Lu
The local coordination structure of metal atoms in single-atom catalysts (SACs) greatly influences their catalytic performance. And for most SACs, single metal atoms were anchored on carbon materials with N or C coordination. However, the rational design of oxygen-containing SACs and analyzing its structure–performance relationship remain challenging. Herein, we used amino-rich compounds to tailor the metatungstate and fix the W atoms and finally obtained the oxygen-containing W-SACs. The structural evolution of tungsten and its coordination atoms were tracked by electrospray ionization high-definition mass spectrometry. Furthermore, aberration-corrected transmission electron microscopy, X-ray absorption fine-structure spectroscopy, and first-principles calculation results revealed that different from the traditional SACs, the WO2N2 moiety (W coordinated with two O atoms and two N atoms) may be the favored structure for W species. This special structure promoted the energy transfer for enhancing singlet oxygen generation. This work presents an efficient way to prepare more high-efficiency SACs by atomic-scale tailoring and structural evolution tracking at the molecular level.
研究领域:
催化化学
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材料科学
·
理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Wang Song,Qianni Cheng,Li Han,Jiawei Ji,Yandi Cai,Wei Tan,Jingfang Sun,Changjin Tang,Lin Dong
Manganese oxide-based catalysts exhibit excellent low-temperature denitration efficiency, making them potential candidates for application. Herein, the relationship between reaction stability and phase structure for MnO 2 , Mn 2 O 3 and Mn 3 O 4 was disclosed. The NO conversion for Mn 2 O 3 drastically reduced after 120 h reaction, while minor decline was detected for MnO 2 and Mn 3 O 4 . Based on dedicate qualitative and quantitative analyses on the deposits over catalyst surface, deactivation trigged by ammonium nitrate (AN) deposition was confirmed. Different from penta-coordinated Mn 4+ on MnO 2 (110) and tri-coordinated Mn 2+ , penta-coordinated Mn 4+ on Mn 3 O 4 (101), the unique tetra-coordinated Mn 3+ on Mn 2 O 3 (200) could stabilize the nitrates and make it difficult to be removed via decomposition or reaction and accumulate continuously, which resulted in the significant deactivation. This research could not only unveil the poisoning mechanism of MnO x based catalysts, but also provide new insights into the relationship between the catalytic stability and surface Mn-O microstructure.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Fengliang Cao,Qingshan Zhao,Xiaojie Tan,Libo Wang,Yikun Zhao,Wei Deng,Linjie Zhi,Mingbo Wu
Optimizing the local environment of metal active centers bonded by nitrogen ligands (M−N 4 ) through additional axial coordination provides a promising approach to enhance the reaction kinetics of heterogeneous catalysis. However, achieving precise targeting and construction of efficient active sites remains a major challenge. In this study, under the guidance of density functional theory (DFT) calculations, we precisely position and engineer atomic Co–N 4 active sites with axial O coordination on porous carbon nanosheets (Co 1 /NOC) for boosted aromatic nitroreduction through a novel template-anchoring strategy. The resulting Co 1 /NOC catalyst exhibited unprecedented catalytic activities towards a series of functionalized nitroaromatics with a record overall turnover frequency (TOF) of 38022 h −1 under mild reaction conditions, 7.6- and 38 times higher than that of Co–N 4 sites (Co 1 /NC) and commercial Pd/C catalysts, respectively, standing ahead of the reported catalysts. Targeted DFT calculations reveal that axial oxygen coordination efficiently promotes the electronic delocalization of the Co center, which dramatically facilitates the formation and utilization of reactive H* species, enhances the selective adsorption of nitroaromatics, and accelerates the conversion of aromatic nitroreduction, eventually attaining exceptional catalytic performance. This work offers a new avenue for precisely tailoring the coordination environment of single-atom catalysts to achieve advanced catalytic performance in chemical transformations.
研究领域:
催化化学
·
材料科学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2025
·
IF 14.9
Dengqi Zhou,Ke Zeng,Liqiang Wang,Feiying Tang
The development of highly efficient non-noble metal catalysts for the hydrogenation of N-heteroarenes under mild condition is of great importance for both theoretical and industrial applications, which can efficiently reduce energy consumption and environmental pollution. In this work, we found that the prepared CoCu nano-alloy catalyst after exposed in the air over 24 h (named Co 1 Cu 1 /C) exhibited a dramatically improved catalytic performance (yield from trace to >99%) for quinoline hydrogenation under mild reaction conditions (60 °C, 3 MPa H 2 ). According to the characterization, the catalyst Co 1 Cu 1 /C exhibited the strong interaction between Co and Cu. Meanwhile, it was endowed with a stable partial oxidation surface. The unsaturated oxygen coordinated surface of Co 1 Cu 1 /C presented a moderate binding for quinoline and 1, 2, 3, 4-tetrahydroquinoline, which could efficiently avoid the deactivation of catalyst and favor the hydrogenation kinetics. The density functional theory (DFT) calculations coupled with X ray-based structural analyses suggested that the unsaturated oxygen coordinated surface could lower the diffusion energy of the active hydrogen species and the reaction barrier for quinoline hydrogenation which resulted from the d - p orbital electron coupling. This work revealed that the catalytic performance of nano-alloy catalysts might not only be ascribed to the interaction between metals, while the unsaturated oxygen coordination of metallic surfaces played an important role.
研究领域:
催化化学
·
材料科学
·
理论化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Tingting Yu,Lei Tao,Zhiyi Liu,Xuge Zhang,Tao Gan,Wensheng Yan,Lirong Zheng,Ge Meng,Wei Chen,Shoujie Liu,Chenliang Ye,Jian Zhang
Unique active sites make single-atom (SA) catalysts promising to overcome obstacles in homogeneous catalysis but challenging due to their fixed coordination environment. Click chemistry is restricted by the low activity of more available Cu(II) catalysts without reducing agents. Herein, we develop efficient, O-coordinated SA Cu(II) directly catalyzed click chemistry. As revealed by theoretical calculations of the superior coordination structure to promote the click reaction, an organic molecule-assisted strategy is applied to prepare the corresponding SA Cu catalysts with respective O and N coordination. Although they both belong to Cu(II) centers, the O-coordinated one exhibits a 5-fold higher activity than the other and even much better activity than traditional homogeneous and heterogeneous Cu(II) catalysts. Control experiments further proved that the O-coordinated SA Cu(II) catalyst tends to be reduced by alkyne into Cu acetylide rather than the N-coordinated catalyst and thus facilitates click chemistry.
研究领域:
化学
·
催化
·
材料科学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Enhao Liu,Yibo Zhu,Shengyong Gao,Junping Hu,Wei Feng,Jisheng Zhou
Achieving superconformal deposition of metallic sodium on 3D matrices is a critical challenge for sodium metal batteries (SMBs). Herein, flexible 3D carbon nanofiber films anchored with axial O-coordinated CuN 4 O 2 single-atom sites (CuN 4 O 2 -CNF) by a ZnCl 2 -mediated thermal activation strategy is designed. Unlike conventional planar CuN 3 configurations obtained without ZnCl 2 , the axial O in CuN 4 O 2 sites exhibits a high density of states near the Fermi level, modulating the electronic structure of neighboring Cu and N. This lowers Na + adsorption energy, accelerates charge transfer and enhances electrolyte permeability, enabling superconformal sodium deposition. As a result, the CuN 4 O 2 -CNF achieves an ultra-low nucleation overpotential of 10 mV, a coulombic efficiency of 99.92% over 8,000 h, and exceptional cycling stability exceeding 10,000 h in symmetric cells. The full coin cells paired with a Na 3 V 2 (PO 4 ) 3 cathode retain 89.5 mA h g −1 after 1,000 cycles at 1 A g −1 and deliver 80.3 mA h g −1 at 5 A g −1 , demonstrating superior rate capability. The pouch cells also maintain a stable capacity of 75.8 mA h g −1 after 150 cycles at 58.5 mA g −1 . These results highlight the transformative potential of axial-coordination for designing high-performance metal batteries, offering insights into interfacial dynamics and host architectures for next-generation energy-storage systems.
研究领域:
储能与转换
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材料科学
·
电化学
·
纳米材料
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电池技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Minzhi Ma,Zeai Huang,Lina Li,Wenda Zhang,Rui Guo,Ruiyang Zhang,Wenjun Fa,Chunqiu Han,Yuehan Cao,Shan Yu,Ying Zhou
The performance of photocatalytic reduction CO 2 to CH 3 OH is intimately tied to the photogenerated electron density of the active center, because CH 3 OH formation involves a 6-electron transfer process. However, the random migration of photocarriers in the photocatalysts is severely not conducive to the directional delivery and enrichment of photogenerated electrons to active sites, leading to poor photocatalytic activity for CO 2 to CH 3 OH. Herein, we reported a coordination environment engineered Pr single-atom catalyst for boosting the photogenerated electron density of the active sites, achieving the high-efficiency photoreduction of CO 2 to CH 3 OH. The carbon nitride (CN) supported Pr single-atom with oxygen coordination was designed via a three-step pyrolysis process . Then, the engineered oxygen coordination configuration for the Pr single-atom (Pr 1 -N 4 O 2 ) was successfully achieved. Importantly, this Pr 1 -N 4 O 2 sites can induce photogenerated electrons more easily to accumulate on the Pr atom as compared to the reference catalyst of the Pr atom without oxygen coordination (Pr 1 -N 6 ). Moreover, the formed atomically dispersed Pr 1 -N 4 O 2 active centers with ultra-high Pr loading (21.05 wt%) can promote CO 2 adsorption and activation, and provide a high density of active sites for CO 2 photoreduction. As a result, the optimized Pr 1 -N 4 O 2 /CN exhibited a boosted photoreduction of CO 2 to CH 3 OH activity (511.1 μmol g −1 h −1 ), which was up to 28.9 and 1.9 times higher than those of CN (17.7 μmol g −1 h −1 ) and Pr 1 -N 6 /CN (274.1 μmol g −1 h −1 ), and preferable to most reported work under similar catalytic conditions. Our findings can provide a fresh prospect for developing innovative SACs to enhance the photoreduction of CO 2 to CH 3 OH activity.
研究领域:
材料科学
·
催化
·
环境化学
·
光化学
✓ 已验证
产品关联
DOI
高影响因子
Carbon Energy
·
2022
·Vol. 5
·期 2
·e216
·
IF 21.556
Jiapeng Ji,Yunpeng Hou,Shiyu Zhou,Tong Qiu,Liang Zhang,Lu Ma,Chao Qian,Shaodong Zhou,Chengdu Liang,Min Ling
The oxygen evolution reaction (OER) activity of single-atom catalysts (SACs) is closely related to the coordination environment of the active site. Oxygen-coordinated atomic metal species bring about unique features beyond nitrogen-coordinated atomic metal species due to the fact that the M–O bond is weaker than the M–N bond. Herein, a series of metal–oxygen–carbon structured low-nucleus clusters (LNCs) are successfully anchored on the surface of multiwalled carbon nanotubes (M-MWCNTs, M = Ni, Co, or Fe) through a foolproof low-temperature gas transfer (300°C) method without any further treatment. The morphology and coordination configuration of the LNCs at the atomic level were confirmed by comprehensive characterizations. The synthetic Ni-MWCNTs electrocatalyst features excellent OER activity and stability under alkaline conditions, transcending the performances of Co-MWCNTs, Fe-MWCNTs and RuO 2 . Density functional theory calculations reveal that the moderate oxidation of low-nucleus Ni clusters changes the unoccupied orbital of Ni atoms, thereby lowering the energy barrier of the OER rate-limiting step and making the OER process more energy-efficient. This study demonstrates a novel versatile platform for large-scale manufacturing of oxygen-coordinated LNC catalysts.
研究领域:
催化
·
电化学
·
材料科学
✓ 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）