CHEMICAL ENGINEERING JOURNAL
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2024
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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
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DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
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
Nature Communications
·
2022
·Vol. 13
·期 1
·1-12
·
IF 17.694
Guo Yalin,Huang Yike,Zeng Bin,Han Bing,AKRI Mohcin,Shi Ming,Zhao Yue,Li Qinghe,Su Yang,Li Lin,Jiang Qike,Cui Yi-Tao,Li Lei,Li Rengui,Qiao Botao,Zhang Tao
Semi-hydrogenation of acetylene in excess ethylene is a key industrial process for ethylene purification. Supported Pd catalysts have attracted most attention due to their superior intrinsic activity but often suffer from low selectivity. Pd single-atom catalysts (SACs) are promising to significantly improve the selectivity, but the activity needs to be improved and the feasible preparation of Pd SACs remains a grand challenge. Here, we report a simple strategy to construct Pd 1 /TiO 2 SACs by selectively encapsulating the co-existed small amount of Pd nanoclusters/nanoparticles based on their different strong metal-support interaction (SMSI) occurrence conditions. In addition, photo-thermo catalysis has been applied to this process where a much-improved catalytic activity was obtained. Detailed characterization combined with DFT calculation suggests that photo-induced electrons transferred from TiO 2 to the adjacent Pd atoms facilitate the activation of acetylene. This work offers an opportunity to develop highly stable Pd SACs for efficient catalytic semi-hydrogenation process.
研究领域:
化学工程
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催化科学
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DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2023
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IF 13.1
Zhongmiao Gong,Zhigang Chen,Hao Li,Guang Yang,Min Yuan,Zhiyun Li,Xueying Wan,Yi Cui
Surface-supported isolated atoms in single-atom catalysts (SACs) grant maximum utilization of metals in heterogeneous catalysis. Herein, we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally melting Pd nanoparticles on an oxygen-vacancy-rich tungsten-oxide matrix at reduction atmosphere. Near ambient pressure X-ray photoelectron spectroscopy was used to monitor the formation of zero-valence Pd single atoms and the increased metallic feature of WO 3− x substrate. Accordingly, the as-obtained zero-valence Pd single-atom catalyst exhibits a markedly boosted HER activity with a low overpotential ( η 10 = 70 mV) at the current density of 10 mA/cm 2 and a small Tafel slope ( b = 68 mV/dec), nearly 150 mV and a 3.0-fold enhancement than those of Pd nanoparticles ( η 10 = 220 mV, b = 133 mV/dec) under the same conditions. In addition, quasi in situ XPS results suggest the hydrogen spillover effect is more likely to occur on Pd single atoms during the electrochemical process. Our work may pave an interesting route for the rational design of highly-efficient single-atom catalyst, and the elucidation of corresponding enhanced reaction mechanisms by the utilization of advanced characterization techniques.
研究领域:
催化化学
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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
Journal of Environmental Sciences
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2024
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IF 5.9
Wei Hou,Qian Zheng,Hengyue Xu,Guangming Zhan,Long Zhao,Jie Dai,Jiaxian Wang,Xingyue Zou,Bing Zhou,Lufa Hu,Ruizhao Wang,Kaiyuan Wang,Yancai Yao,Lizhi Zhang
Atomic hydrogen (H*) plays a crucial role in electrochemical reduction technology towards various environmental and energy applications, but suffers from low utilization efficiency arisen from the undesirable H–H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites. Herein, we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd 1 -O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H* utilization site, which synchronously inhibits the H–H dimerization and the competitive adsorption of water molecule and targeted reactants. Experiments and theoretical calculations revealed that the Ti–O sites could synergistically dissociate water to H*, which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate. These Pd 1 -O-Ti dual sites delivered almost 100 % bromate reduction efficiency with a rate constant of 1.57 h –1 , far superior to those of Pd n -O-Ti with adjacent Pd sites (0.52 h –1 ), Pd 1 -N-C with single sites (0.04 h –1 ) and commercial Pd/C (0.18 h –1 ), respectively. This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions, and provide new insights in improving H* utilization for environmental remediation.
研究领域:
环境科学
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材料科学
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电化学
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产品关联
DOI
PubMed
高影响因子
ACS Catalysis
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2024
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IF 11.3
Xin Li,Jiaqi Liu,Jianguo Wu,Lipeng Zhang,Dong Cao,Daojian Cheng
Fabricating highly active catalysts with fully exposed metal atoms is necessary to greatly enhance the catalytic efficiency of selective hydrogenation. Here, we precisely constructed a carbon-nitride-nanosheet-supported fully exposed Pd atomically dispersed catalyst (PdSA+C/g-C3N4) by a simple low-temperature impregnation strategy. Importantly, the obtained PdSA+C/g-C3N4 includes Pd–N3 single atoms and Pd subnanoclusters with atomic-layer thickness. Moreover, the PdSA+C/g-C3N4 exhibits a 100% cinnamaldehyde (CAL) conversion rate and a 97.3% phenylpropanal selectivity during the CAL hydrogenation, which is much better than most of the reported catalysts. Meanwhile, the turnover frequency of PdSA+C/g-C3N4 is 9.19 s–1, about 12 times higher than that of Pd single-atom catalysts. Further mechanism studies show that the synergistic effect between Pd–N3 single atoms and fully exposed Pd subnanoclusters in PdSA+C/g-C3N4 is the key to improve the selective hydrogenation activity of CAL. Specifically, hydrogen preferentially adsorbs and dissociates on Pd nanoclusters, while CAL preferentially adsorbs on Pd single atoms. After that, hydrogen could overflow from Pd clusters to Pd single atoms during the CAL hydrogenation, thus improving the reaction kinetics. This work develops a simple method to prepare catalysts with multimetal synergistic sites and provides an insight into the synergistic mechanism of atomically dispersed catalysts during hydrogenation reaction.
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
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
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2024
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IF 11.2
Nuo Xu,Haoran Zhou,Mingqiang Zhang,Yuchuan Ye,Kaiwen Wang,Yingtang Zhou,Yunfeng Zhu,Yao Zhang
Hydrogen storage plays a pivotal role in the hydrogen industry, yet its current status presents a bottleneck. Diverse strategies have emerged in recent years to address this challenge. MgH 2 has stood out as a promising solid-state hydrogen storage material due to its impressive gravimetric and volumetric hydrogen density, but its practical application is hampered by elevated thermal stability and sluggish kinetics. In this study, we introduce a solution by synthesizing Pd metallene through a one-pot solvothermal method, revealing a distinctive highly curved lamellar structure with a thickness of around 1.6 nm. Incorporating this Pd metallene into MgH 2 results in a composite system wherein the starting dehydrogenation temperature is significantly lowered to 439 K and complete dehydrogenation occurs at 583 K, releasing 6.14 wt.% hydrogen. The activation energy of dehydrogenation for MgH 2 was reduced from 170.4 kJ mol –1 to 79.85 kJ mol –1 after Pd metallene decoration. The enthalpy of dehydrogenation of the MgH 2 –10 wt.% Pd sample was calculated to be 73 kJ mol –1 H 2 –1 and decreased by 4.4 kJ mol –1 H 2 –1 from that of dehydrogenation of pure MgH 2 (77.4 kJ mol –1 H 2 –1 ). Theoretical calculations show that the average formation energy and average adsorption energy of hydrogen vacancies can be significantly reduced in the presence of both Pd clusters and Pd single atoms on the surface of MgH 2 /Mg, respectively. It suggests that the synergistic effect of in situ formed Pd single atoms and clusters significantly improves the hydrogenation and dehydrogenation kinetics. The identified active sites in this study hold potential as references for forthcoming multi-sized active site catalysts, underscoring a significant advancement toward resolving hydrogen storage limitations.
研究领域:
材料科学
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能源存储
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催化化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Yunhua Li,Shiyu Zheng,Yuting He,Shui Yang,Wei-Hsiang Huang,Chih-Wen Pao,Zhiwei Hu,Xiaoqing Huang
The coordination environments of isolated metals significantly influence the catalytic properties of materials. However, challenges persist in the precise modulation of these microenvironments. In this study, we achieved atomically dispersed Pd on sulfur-doped tin dioxide (SnO 2 ) through the controlled oxidation of SnS 2 nanosheets pre-loaded with single-atom Pd (Pd/SnS 2 ). Our findings reveal that the synthesized catalyst features a central single-atom Pd, which coordinates with oxygen and tin in the first coordination shell and sulfur binding tin in the second shell. The coordination of isolated Pd with sulfur in the out-of-plane second shell layer enhances oxygen adsorption while inhibiting O O dissociation, thus directing hydrogen peroxide selectivity. This results in a higher productivity and durability of hydrogen peroxide compared to pristine Pd/SnS 2 and traditional samples. This work presents an effective strategy to tailor and preserves the coordination micro-environment of central single-atom metals during catalytic reactions.
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
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2025
·
IF 3.9
Xinyue Zhang,Yuan Yao,Yingying Cao,Xin Tan,Xiaomin Fang,Yanqiang Zhang
The high strain energy of the three-membered ring can increase the combustion calorific value of space fuels. At present, the cyclopropanation of alkenes is the bottleneck to obtain highly-energy three-member-ring fuels. In this article, Pd single-site catalysts (SSCs) were prepared to catalyze the cyclopropanation of norbornene. Pd2+ on the SSCs enhanced the adsorption of CH2N2 through electrostatic interaction, efficiently forming metal carbene. The conversion and selectivity of norbornene cyclopropanation reached 99.9% and 96.9%, which are much higher than those of commercial Pd/C (conversion 42.3%, selectivity 80.8%). In addition, the obtained tricyclooctane shows excellent properties (density 0.93 g/cm3, calorific value 42.75 MJ/kg) to be a promising high-performance rocket fuel. This work provides an efficient method for the synthesis of cyclopropane-based space fuels from alkenes.
研究领域:
化学
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材料科学
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能源科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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IF 24.319
Zhijun Li,Mingyang Zhang,Xiuli Dong,Siqi Ji,Lili Zhang,Leipeng Leng,Honghong Li,J. Hugh Horton,Qian Xu,Junfa Zhu
The realization of efficient and fully controllable synthesis of single atom catalysts is an exciting frontier, yet still challenging in the modern catalysis field. Here we describe a straightforward high-temperature quenching approach to precisely construct isolated palladium atoms supported over cubic indium oxide, with individual palladium atoms coordinated with four neighboring oxygen atoms. This palladium catalyst achieves exceptional catalytic efficiency in the selective hydrogenation of nitrobenzene to aniline, with more than 99% chemoselectivity under almost 100% conversion. Moreover, it delivers excellent recyclability, anti-CO poisoning ability, storage stability, and substrate tolerance. DFT calculations further reveal that the high catalytic activity stems from the optimized electronic structure and the charge states of palladium atoms in the defect-containing indium oxide. Our findings provide an effective approach to engineering single atom catalysts at the atomic level and open the door to a wide variety of catalytic reactions .
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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产品关联
DOI
高影响因子
Nano Research
·
2021
·Vol. 14
·期 11
·4347-4355
·
IF 8.897
Lu Xiaowen,Guo Chunmu,Zhang Mingyang,Leng Leipeng,Horton J. Hugh,Wu Wei,Li Zhijun
Chemoselective hydrodeoxygenation of vanillin is of great importance in converting biomass into high value-added chemicals. Herein, we describe a facile photochemical route to access palladium single atoms and clusters supported on silicoaluminophosphate-31 (SAPO-31) as a highly active, chemoselective, and reusable catalyst for hydrodeoxygenation of vanillin. Characterizations by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and CO-absorbed diffuse reflectance infrared Fourier transform spectroscopy reveal the atomically dispersed palladium single atoms and clusters are loosely bonded and randomly dispersed, without forming strong palladium-palladium metallic bonding, over the SAPO-31 support. This catalyst, with a full metal availability to the reactants, exhibits exceptional catalytic activity (TOF: 3,000 h −1 , Yield: > 99%) in the hydrodeoxygenation of vanillin toward 2-methoxy-4-methylphenol (MMP) under mild conditions (1 atm, 80 °C, 30 min), along with excellent stability, scalability (up to 100-fold), and wide substrate scope. The superior catalytic performance can be attributed to the synergistic effect of the positively charged palladium single atoms and fully exposed clusters, as well as the strong metal-support interactions. This work may offer a new avenue for the design and synthesis of fully exposed metal catalysts with targeted functionalities.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
Journal of Materials Chemistry A
·
2017
·Vol. 5
·期 43
·22618-22624
·
IF 8.867
Dong Wang,Xin Wang,Yue Lu,Changsheng Song,Jie Pan,Chilin Li,Manling Sui,Wei Zhao,Fuqiang Huang
Noble metal catalysts have extraordinary catalytic activity but suffer from high cost; therefore single atom catalysis attracts tremendous attention. Here, we propose atom-scale dispersed palladium (Pd) in a layered TaS2 lattice to form new compounds of PdxTaS2, whose crystal structure was resolved by powder X-ray diffraction. The electrical conductivity of metallic Pd0.1TaS2 (1.36 × 104 S m−1) is twice as large as that of TaS2 (6.18 × 103 S m−1). This compound applied as a new electrocatalyst for the hydrogen evolution reaction (HER) exhibits excellent catalytic performance with an onset overpotential of 77 mV, superior to those of other catalysts such as TaS2 (295 mV) and Pd-loaded TaS2 (114 mV). Density functional theory calculations reveal that the interaction of Pd-4d and Ta-5d orbitals results in the upshift of the Fermi level (TaS2versus Pd0.1TaS2) to decrease the barrier height for the HER. Furthermore, the hybridization of Pd-4d and S-3p orbitals builds up pathways along the c axis to improve the conductivity and promote HER performance. It is noted that the amount of Pd used in Pd0.1TaS2 is only 4 wt%, compared with 20 wt% in commercial Pd/C catalysts, which is beneficial for its practical application.
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
高影响因子
危险品化学品经营许可证（带存储）