Energy & Environmental Materials
·
2021
·Vol. 6
·期 1
·e12292
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IF 15.122
Ruofan Shen,Yanyan Liu,Hao Wen,Xianli Wu,Zhikun Peng,Sehrish Mehdi,Tao Liu,Huanhuan Zhang,Shuyan Guan,Erjun Liang,Baojun Li
The dissociation of water is the rate-determining step of several energy-relating reactions due to high energy barrier in homolysis of H-O bond. Herein, engineering vacancy-atom ensembles via injecting oxygen vacancy (V O ) into single facet-exposed TiO 2 -Pd catalyst to form V O -Pd ensemble is proposed and implemented. The outstanding activity of as-prepared catalyst, 1.5-PdTV O , toward water dissociation is established with a turnover frequency of 240 min −1 in ammonia borane hydrolysis at 298 K. Density functional theory simulation suggests that the V O -Pd ensemble is responsible for the high intrinsic catalytic activity. Water molecules tend to be dissociated on V O sites and ammonia borane molecules on Pd atoms. Those H atoms from water dissociation on V O combine with H atoms from ammonia borane on Pd atoms to generate H 2 . This insights into engineering vacancy-atom ensembles catalysis provide a new avenue to design catalytic materials for important energy chemical reactions.
研究领域:
材料科学
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催化化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
He Jiang,Haoliang Wei,Xinkai Li,Yijun Zhang,Tingjiang Lu,Feili Li,Shuang Song,Yan Yu,Meilan Pan,Weiting Yu
The widespread discharge of halogenated organic pollutants (HOPs) in wastewater brings significant risks to the environment and human health due to potent high toxicity, antibacterial activity, and strong biodegradation resistance. Adsorbed atomic hydrogen (H* ads )-mediated electrocatalytic hydrodehalogenation (EHDH) has been recognized as an efficient strategy for HOPs removal through selectively breaking carbon-halogen bonds. In this work atomic Pd uniformly anchored on molybdenum disulfide (denoted as Pd-MoS 2 ) was synthesized through a facile hydrothermal method and found with state-of-the-art specific activity in florfenicol (FLO) removal via the H* ads -mediated EHDH process. Pd-MoS 2 completely dehalogenated (∼100 %) FLO within 30 min at a rate constant of 0.15 min −1 , which was 6.0, 6.5 and 33.1 times the value of MoS 2 , Pd/C and carbon paper samples, respectively. Notably, the toxicity of the wastewater was reduced to 1/6 of its original value after the treatment. Moreover, Pd-MoS 2 presented superior catalytic stability in five successive cycles. Furthermore, Pd-MoS 2 was also robust in complex water environment with practical applicability for industrial wastewater treatment. A dual-active-center mechanism with enhanced H* ads production capacity and the improved H* ads utilization efficiency was contributed to the increased EHDH activity on Pd-MoS 2 .
研究领域:
环境科学
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材料科学
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化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2020
·
IF 4.65
Minglu Li,Chaozhu Shu,Anjun Hu,Jiabao Li,Yu Yan,Miao He,Jianping Long
Lithium-oxygen batteries (LOBs) are considered to be one of the most competitive energy storage devices due to their high theoretical energy density . However, challenges including poor catalytic activity and durability of the oxygen electrode seriously hinder the in-depth development of LOBs. Adjusting the surface electronic structure of the oxygen electrode provides a new prospect for realizing highly efficient electrocatalysts . In this contribution, we report that atomic-scale palladium (Pd) involving in MoSe 2 (Pd–MoSe 2 ) is capable of adjusting the in-plane electron density of MoSe 2 via spontaneous interface chemical reactions, thereby accelerating the electron migration along the in-plane direction. The synergy between the created Se vacancies and Pd atoms can further increase the electroactive sites on the Pd–MoSe 2 surface, which is conducive to improving the catalytic activity of the electrode and thereby accelerating the kinetics of oxygen electrode reactions. The results show that Pd–MoSe 2 based LOBs exhibit excellent electrochemical performance such as high Coulombic efficiency (97.81%) as well as extended cycle life (1952 h). This work shows that the adjustment of in-plane electron density by exotic metal atom is a viable strategy to improve the catalytic activity of layered transition metal selenide, which provides the possibility of developing highly efficient electrocatalysts for LOBs.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
ACS Nano
·
2025
·
IF 16
Xiuling Guo,Chao Feng,Zihao Yang,Shingo Hasegawa,Ken Motokura,Yong Yang
Engineering the local coordination environment of single metal atoms is an effective strategy to improve their catalytic activity, selectivity, and stability. In this study, we develop an asymmetric Pd–Ag diatomic site on the surface of g-C3N4 for the selective electrocatalytic semihydrogenation of alkynes. The single Pd atom catalyst, which has a locally symmetric Pd coordination, was inactive for the semihydrogenation of phenylacetylene in a 1 M KOH and 1,4-dioxane solution at an applied potential of −1.3 V (vs RHE). In sharp contrast, doping Ag sites into single Pd atom catalyst to form paired Pd–Ag diatomic sites with asymmetric Pd coordination substantially enhanced the reaction, resulting in a high conversion (>98%) with exceptional time-independent selectivity to styrene under identical conditions. Characterization and theoretical calculations reveal that the introduction of a Ag site into single Pd atoms disrupts their symmetry coordination by forming Pd–Ag bonds with N2–Pd–Ag–N configuration, thereby modulating the electronic and geometric structures of Pd sites, which in turn benefits the adsorption and activation of substrate and lowers energy barrier for the rate-determining step of semihydrogenation, ultimately enhancing the electrocatalytic reaction. This work provides a facile and powerful strategy for the design of advanced catalysts by tuning the local coordination environment for selective catalysis.
研究领域:
材料科学
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催化化学
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产品关联
DOI
PubMed
高影响因子
Nano Research
·
2021
·Vol. 15
·期 4
·3114-3121
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IF 8.897
Li Zhijun,Leng Leipeng,Lu Xiaowen,Zhang Mingyang,Xu Qian,Horton J. Hugh,Zhu Junfa
Atomically dispersed single atom catalysts represent an ideal means of converting less valuable organics into value-added chemicals of interest with high efficiency. Herein, we describe a facile synthetic approach to create defect-containing β -FeOOH doped with isolated palladium atoms that bond covalently to the nearby oxygen and iron atoms. The presence of singly dispersed palladium atoms is confirmed by spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements. This single palladium atom catalyst manifests outstanding catalytic efficiency (conversion: 99%; selectivity 99%; turnover frequency: 2,440 h −1 ) in the selective hydrogenation of cinnamaldehyde to afford hydrocinnamaldehyde. Experimental measurements and density functional theory (DFT) calculations elucidate the high catalytic activity and the strong metal-support interaction stem from the unique coordination environment of the isolated palladium atoms. These findings may pave the way for the facile construction of single atom catalysts in a defect-mediated strategy for efficient organic transformations in heterogeneous catalysis.
研究领域:
催化化学
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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
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Zhijun Li,Honghong Li,Dundong Yuan,Leipeng Leng,Mingyang Zhang,Minghui Di,J. Hugh Horton,Jun Wang,Litao Sun,Weiwei Sun
Exploring the interaction between metal and support is of great importance in enhancing the catalytic performance and deepening the mechanistic understanding of single atom catalysis. Here we describe a photoinduction method to construct atomically dispersed palladium atoms supported over defect-containing boehmite (γ-AlOOH) nanoleaf with a palladium loading of 0.32 wt%. The existence of singly dispersed palladium atoms is confirmed by spherical aberration correction electron microscopy, extended X-ray absorption fine structure measurement, and CO-absorbed diffuse reflectance infrared Fourier transform spectroscopy. This catalyst shows excellent catalytic efficiency in trans -stilbene epoxidation to yield trans -stilbene oxide (TOF: 416 h −1 ; conversion: 84 %; selectivity: 99 %), along with excellent recyclability and scalability. In addition, various aromatic olefins were successfully transformed into the corresponding epoxides with high selectivity and excellent yield. DFT study further reveals that the high catalytic activity originates from under-coordinated single palladium atoms in the defect-containing γ-AlOOH in a unique coordination environment. This lays the foundation for the facile creation of single atom catalysts and sheds light on the possibility for scale-up production.
研究领域:
催化化学
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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
Journal of Materials Chemistry A
·
2020
·Vol. 8
·期 37
·19300-19308
·
IF 11.301
Jingchun Wang,Xiaoyu Qiu,Keying Su,Siyuan Wang,Jiatian Li,Yawen Tang
It remains a grand challenge to control the island growth mode because a conformal growth is theoretically more favorable, in which the lattice mismatch between the overlayer and the substrate is negligible. Herein, we report the first example of “Frank–van der Merwe” mode and “Volmer–Weber” mode of Pd atoms on Boerdijk–Coxeter-type helical Au(111) nanowires. Quantitative analyses suggest that the pH-induced faster kinetic reduction rate (1.2 × 10−2 s−1) is a crucial factor to switch the Pd-growth mode from the conformal 4-atom-layers to ultrasmall islands. As a proof-of-concept application, the VW Au@Pd HNWs exhibit outstanding ORR activity (Eonset = 1.07 V, E1/2 = 0.91 V) and stability, outperforming FM Au@Pd NWs, Au(111) NWs, Pd black, and most reported electrocatalysts. Physical characterization systematically elucidated similar components, d-band center locations, and lattice distortions of both the representative structures, giving brand-new insights into the impact of their slightly different surface microstructures. In particular, the segmented oxyphilic–anaerobic interface of the VW Au@Pd HNWs directly balances the adsorbability of the intermediates; meanwhile, the interleaved lattice orientations favor multi-directional electron transmissions to promote ORR kinetics. This finding not only challenges the conventional wisdom of lattice-matched growth but also provides an identical model for the in-depth understanding of the structure–function relationship with a focus on the growth modes.
研究领域:
材料科学
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电化学
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催化作用
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
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IF 9.4
Yao Xiao,Cuiying Tan,Fangui Zeng,Wengang Liu,Jian Liu
Molybdenum sulfide materials have long been considered as attractive non-precious-metal electrocatalysts for the hydrogen evolution reaction (HER). However, comparing with the crystalline counterpart, amorphous MoS x has been less investigated previously. We here propose to increase the catalytical activity of a-MoS x by raising the reactant concentration at the catalytic interface via a chemical doping approach. The reconstruction of coordination structure of a-MoS x via Pd doping induces the formation of abundant unsaturated S atoms. Moreover, the reactant friendly catalytic interface is constructed through introducing hydrophilic groups to a-MoS x . The doped a-MoS x catalyst exhibits significantly enhanced HER activity in both acid and alkaline media.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2020
·
IF 0
Jun Wang,Qing Kuang,Xiaofang Su,Xiaowen Lu,Leipeng Leng,Mingyang Zhang,Chunmu Guo,Tong Li,Qian Xu,Shuhui Sun,J. Hugh Horton,Wei Wu,Zhijun Li
Supported single-atom catalysts have become one of the most exciting frontiers in heterogeneous catalysis. The physicochemical properties of these materials are highly interesting; however, the generation of stable single atoms on solid supports is still challenging. Herein, we report an efficient and operationally simple postsynthesis method, consisting of spatial confining, freeze-drying, and reducing steps, for the construction of singly dispersed palladium atoms on SAPO-31 (Pd1/SAPO-31) with promising application prospects in the semihydrogenation of alkynes. A typical Pd–N–C single-atom catalyst derived from the ZIF-8-supported palladium complex was prepared and compared to Pd1/SAPO-31. The Pd1/SAPO-31 catalyst showed outstanding performance in the semihydrogenation of both phenylacetylene (85% selectivity at 99% conversion, 40 min) and 1-chloro-4-ethynylbenzene (95% selectivity at 99% conversion, 60 min). In addition, this single-atom palladium catalyst was highly active in triethoxysilane oxidation. Most importantly, this catalyst retained its atomic dispersion and catalytic activity after high-temperature thermal treatment in Ar at 700 °C. This study demonstrates how zeolites can be used to confine atomically dispersed metal species and tune the activity and stability of these materials to meet the needs of practical applications.
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
CARBON
·
2022
·
IF 11.307
Lizhen Hu,Teng Wang,Qianqian Nie,Jiayou Liu,Yunpei Cui,Kefei Zhang,Zhongchao Tan,Hesheng Yu
Efficient, stable, and selective photocatalytic conversion of nitric oxide (NO) into nitrogen dioxide (NO 2 ) is highly desirable but remains a big challenge. We prepare single atom catalyst (SAC) by anchoring single Pd atoms onto graphitic carbon nitride (CNPd) via chemical impregnation followed by calcination . The prepared CNPd SAC is confirmed by aberration-correction high-angle-annular-dark field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy. The synthesized SAC outperforms its competitors reported earlier for photocatalytic removal of NO under visible light and simulated sunlight irradiation in terms of selectivity and stability. The SAC maintains a NO removal efficiency of 83% and an instantaneous selectivity for NO 2 of 92.8% over 117.6 h under simulated sunlight with the inlet NO concentration of 12 ppm. This duration is about 23.5 times the longest duration tested for other catalysts in the literature. The experimental results and density functional theory (DFT) calculations reveal that single Pd atom promotes the photocatalytic degradation of NO. Moreover, the DFT calculations prove that the nitrate ions that accumulate on the surface of the SAC can react with NO to produce NO 2 . This reaction enhances the selectivity for NO 2 and stability of the SAC.
研究领域:
环境科学
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材料科学
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化学
✓ 已验证
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2022
·Vol. 29
·期 16
·e202203142
·
IF 5.02
Jingwen Luo,Anqi Huang,Yao-Yue Yang,Xing-Yu Ma,Quan-Liang Chen,Junxian Chen,Yajuan Wu
Graphical Put to good use : A Pd-doped Co (Pd/Co) catalyst with high Pd atom utilization efficiency was designed and prepared for hydrogenation of nitroarenes. Its catalytic activity was much better than commercial Pd powder (>150 times) in nitrobenzene hydrogenation reaction. This work might provide a simple and low-cost methodology to design and synthesize highly efficient catalysts. Enhancing catalytic performance as well as reducing catalyst cost are the eternal pursuit for the catalysis community. Herein, a simple and effective palladium-doped cobalt (Pd / Co) catalyst with high Pd atom utilization efficiency was synthesized via galvanic replacement reaction for the selective hydrogenation of nitrobenzene with H 2 at room temperature, delivering >99 % yield of aniline with up to 158 times higher catalytic activity than commercial palladium powder. Detailed characterizations and DFT calculations revealed that Co−Pd interaction leads to a decrease in electron density of Pd and the distance between Pd atoms that results in the enhanced catalytic performance. Further experiments indicated that the Pd / Co catalyst serves as a highly efficient, selective, and recyclable catalyst for a range of nitroarene substrates. This work might provide a green and sustainable methodology to design and synthesize highly active catalysts with high utilization efficiency of the noble metals in fundamental and applied research.
研究领域:
催化化学
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材料科学
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理论计算化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Cell Reports Physical Science
·
2020
·
IF 0
Nating Yang,Yonghui Zhao,Hao Zhang,Weikai Xiang,Yuhan Sun,Shuai Yang,Yu Sun,Gaofeng Zeng,Kenichi Kato,Xiaopeng Li,Miho Yamauchi,Zheng Jiang,Tong Li
Sintering-induced aggregation of active metals is a major cause of catalyst deactivation. Catalysts that can operate above 800°C are rare. Here, we report an unusual noble metal catalyst with sintering-induced activation at temperatures up to 1,000°C. The catalyst consists of atomically dispersed palladium embedded in a reducible SnO 2 support designated for lean methane combustion. High temperature reaction simultaneously causes favorable changes of palladium ensemble state combining synergistically with lattice oxygen activation. Such changes lead to at least one order of magnitude improvement of the intrinsic reactivity, which compensates the surface area loss. Extensive characterizations such as atom probe tomography, X-ray absorption spectroscopy, and isotope tracking together with theoretical calculations illustrate the structure and surface chemistry changes and their impacts on the reaction mechanism. The catalyst also shows notable long-term stability and facile regeneration after poisoning. Our work may provide new insights into designing active and thermally stable catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
危险品化学品经营许可证（带存储）