ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Ran Zhang,Liye Zhu,Xuan Liu,Jiayin Zhu,Yan Zhao
Owing to the increasing energy demands, direct small-molecule fuel cells, such as ethanol and formate fuel cells, have attracted great attention. During the operation of the fuel cell, noble metal catalysts are widely used to accelerate the reaction kinetics by alloying with other materials. However, there are a few facile methods for improving elemental metal catalytic activity. In this work, the defect-rich palladium (Pd) aerogels are acquired by laser ablating technology, which can significantly improve the intrinsic activity of Pd elementary catalysts through introducing defects and lattice strain. The electrochemical results show that the mass and specific activities of the obtained Pd aerogel for the formate oxidation reaction are 2.26 and 1.99 times higher than those of the commercial Pd/C. The excellent activity and stability of the Pd aerogel for ethanol oxidation reaction have also been demonstrated. The effect of the compressive strain is further investigated by density functional theory (DFT) calculations. It has been found that the compressive strain weakens the adsorption strength of the intermediates, which can facilitate the desorption of toxic specifics. The laser-assisted synthesis of defect-rich aerogel paves a way in optimizing the structure of the elemental metal catalysts and improving their intrinsic catalytic activity.
研究领域:
材料科学
·
电化学
·
催化
·
燃料电池
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DOI
高影响因子
Catalysis Science & Technology
·
2018
·Vol. 8
·期 7
·1858-1866
·
IF 5.365
Qingjie Meng,Jiajia Liu,Xiaole Weng,Pengfei Sun,Jawwad A. Darr,Zhongbiao Wu
Noble metals, e.g. Pd, are often made into hybrid or composite catalysts (with less expensive materials) to oxidize industry-source emitted volatile organic compounds (VOCs) at low temperatures. In general, the loadings of these metals should be optimized to reduce costs whilst maintaining activity. There exists the possibility to obtain highly active catalysts with low loadings of noble metals by properly tuning the valence state of the metal(s). However, the relationship between the valence state and its effect on catalyst performance is still a matter of debate. In this article, we used supercritical water (sc-H2O), in the presence of oxidizing or reducing gases, as a feasible reaction medium to synthesize Pd/NiO hybrid nano-catalysts and in situ modify the valence state of Pd. After subjecting the catalysts to a range of analytical techniques, including XRD, H2-TPR, DRIFT, TPSR, etc., we unveiled that Pd0 is more active than PdOx and metal oxides in the catalytic oxidation of toluene. This is mainly because the stabilized Pd0 is capable of activating gaseous oxygen (and toluene) at low temperatures and returning to the original state by toluene even with excess oxygen. Although PdOx could desorb active oxygen under a reducing atmosphere and might assist in the oxygen spillover from NiO, it is difficult to convert into Pd0 in an oxygen-rich environment. The developed Pd0-dominated catalyst was found to be robust and highly active after an ageing test with and without water vapour.
研究领域:
催化化学
·
环境科学
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DOI
高影响因子
RSC Advances
·
2014
·Vol. 4
·期 63
·33347-33354
·
IF 3.708
Tieyong Xu,Qunfeng Zhang,Dahao Jiang,Qiuxia Liang,Chunshan Lu,Jie Cen,Xiaonian Li
Sulfur deactivation is a serious problem which largely limits the industrial application of noble metals as catalysts. Here we report a thermal oxidation method to regenerate sulfone poisoned Pd/C catalyst applied in the hydrogenation of sodium-m-nitrobenzene sulfonate (SNS). It was found that the initial activity of Pd/C catalyst could be substantially recovered after treating it in air at temperatures as low as 100 °C. And the catalyst could be reused for at least 20 times without the significant loss of activity. The properties of deactivated and regenerated catalysts were studied in detail by BET measurement, X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD), and Fourier transform infrared spectroscopy (FT-IR). The results indicated that the main surface sulfur species found on deactivated and regenerated Pd surfaces were Sn and sulfate (SO4), respectively. The change of the valence of sulfur species was found to be the key factor influencing the catalytic activity of the Pd-based catalyst.
研究领域:
化学工程
·
催化科学
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2020
·
IF 5.006
Caoping Yang,Kaijie Li,Junyou Wang,Shenghu Zhou
Pd nanoparticles (NPs) encaged hollow mesoporous silica nanoreactors (Pd@HMSNs) are prepared for hydrogenations of phenol, cresols and chlorophenols to cyclohexanone derivatives. Pd@HMSNs feature ∼ 4 nm Pd NPs in ∼ 16 nm hollow cavities of ∼ 30 nm HMSNs. Such Pd@HMSNs are highly thermally and catalytically stable. At mild reaction conditions, Pd@HMSNs efficiently catalyze hydrogenations of phenol and m -cresol to cyclohexanone derivatives with ≥ 98.3 % selectivity at ≥ 99.0 % conversions. Hydrogenations of o - and m -chlorophenol over Pd@HMSNs give cyclohexanone with ≥ 97.3 % selectivity at 100.0 % conversions, demonstrating a beneficial effect of such HMSNs for consecutive reactions. The confinement of Pd NPs inside hollow cavities of mesoporous nanoreactors greatly promotes collision times of reactant molecules with Pd NPs, resulting in an enhanced catalytic efficiency, while the residence of Pd NPs inside cavities provides a protecting effect for Pd NPs and is beneficial to thermal and catalytic stabilities.
研究领域:
催化
·
纳米技术
·
化学工程
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DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2026
·
IF 19.9
Ou Wang,Leiyu Diao,Ping Li,Youyou Feng,Dong Cheng,Yaqiong Su,Jing Wei
Pd-based nanoparticles have been widely employed to enhance H 2 sensing performance due to their strong capability for H 2 adsorption and dissociation. However, strong Pd–H* interactions hinder the hydrogen spillover process, while pronounced CO adsorption results in poor selectivity. Herein, we propose a Pt–Pd single-atom alloy (SAA) sensitization strategy that creates electron-deficient Pd δ+ sites to modulate the interaction between Pd and gas molecules. As a proof of concept, Pt 1 Pd SAA is deposited on commercial SnO 2 to fabricate H 2 sensors. The resulting device achieves an ultra-low detection limit (21 ppb), short response and recovery time (0.8 s and 5.9 s), excellent selectivity and enhanced CO resistance, outperforming traditional Pd nanoparticles, PtPd alloy sensitizers modified SnO 2 gas sensors, and commercial H 2 sensors. Mechanistic studies establish that atomic Pt induces electron-deficient Pd δ+ sites, achieving atomic-scale decoupling of hydrogen activation from CO adsorption, which enables barrierless hydrogen spillover and inherently CO-resistance H 2 sensing, with CO back-donation suppressed by nearly 50%. This study presents a robust SAA sensitization strategy that leverages atomic-level modification-induced electronic structure modulation to overcome the sensitivity-selectivity trade-off, demonstrating its promise for next-generation H 2 sensors.
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Ruiying Xie,Feng Zhang,Guishan Hu,Mengzhen Chen,Huixian Wang,Xiaoquan Feng,Xuerui Wang,Yatao Zhang,Meixia Shan
The widespread presence of toxic nitroaromatic compounds in industrial effluents demands advanced remediation strategies. Catalytic reduction is highly effective, while the practical application of powdered catalysts is limited by challenges in recovery and reuse. To overcome this issue, macroscopic Pd@NH 2 -MIL-101/AOPIM-1 porous composite beads were fabricated via a phase inversion method, combining the high surface area of NH 2 -MIL-101 with the excellent processability of amidoxime-functionalized polymers of intrinsic microporosity (AOPIM-1). The incorporation of NH 2 -MIL-101 enriches the composite with amino functional groups, thereby enhancing the adsorption and local enrichment of reactants. Furthermore, these nitrogen-rich sites provide robust anchoring points for the uniform dispersion of Pd nanoparticles, collectively boosting catalytic activity and structural stability. The beads exhibited outstanding catalytic activity for the reduction of nitroaromatics, achieving 99% conversion of 4-nitrophenol (4-NP) within 5 min. The catalyst also maintained excellent structural stability over multiple cycles and allowed easy separation. Furthermore, the catalyst exhibited over 90% efficiency in the reduction of other common nitroaromatic pollutants, underscoring its versatility and applicability in wastewater treatment. This work provides a sustainable and practical solution for wastewater treatment by transforming hazardous contaminants into valuable aromatic amines using an easily separable catalytic system.
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产品关联
DOI
高影响因子
RARE METALS
·
2026
·
IF 11
Fan Xue,Liang Chen,Xindong Zhu,Jianrong Zeng,He Zhu,Si Lan
en This link goes to a English section zh This link goes to a Chinese section Precise control of chemical ordering in bimetallic nanocatalysts offers a route to decouple activity and selectivity in acetylene hydrogenation, but direct atomic-scale evidence linking surface order to catalytic performance is scarce. Here, we tune Pd-Cu nanoalloys from chemically disordered to highly ordered states by composition control and targeted H 2 thermal treatment. Under near-industrial conditions, all catalysts reach full acetylene conversion between 100°C and 120°C, whereas the ethylene selectivity enhances with the chemical ordering increasing. By combining synchrotron X-ray absorption fine structure (XAFS) with X-ray total scattering and reverse Monte Carlo (RMC) simulation, three-dimensional atomic models are reconstructed to quantitatively map surface coordination. Compared with the chemically disordered Pd-Cu nanocatalyst, the highly ordered PdCu shows an increase in average surface Pd-Cu coordination and an expansion of mean surface Pd-Pd separations. These structural features weaken ethylene binding and suppress re-adsorption, rationalizing the enhanced selectivity. Our study provides direct atomic-scale evidence connecting chemical order to catalytic selectivity and opens the way for guiding the precise design of bimetal nanocatalysts. 摘要 en This link goes to a English section zh This link goes to a Chinese section 精准调控双金属纳米催化剂的化学有序,可为乙炔加氢反应中活性与选择性的解耦提供有效路径。然而将表面有序度与催化性能直接关联的原子尺度证据仍较为缺乏。本研究通过成分调控与氢气热处理,成功实现了Pd-Cu纳米合金从化学无序态到高度有序态的转变。在近工业条件下,所有催化剂均在100–120°C区间内实现乙炔完全转化,而乙烯选择性随化学有序度的提升显著增强。结合同步辐射X射线吸收精细结构谱、X射线全散射及反向蒙特卡洛(RMC)模拟,我们重构了纳米合金的三维原子结构模型,实现了表面配位环境的定量解析。与化学无序的Pd-Cu纳米催化剂相比,高度有序的PdCu合金表现出更高的表面Pd–Cu配位数和更长的平均Pd–Pd键距。这些结构特征有助于弱化乙烯吸附并提高其选择性。本研究为化学有序与乙烯选择性之间的关联提供了直接的原子尺度证据,为双金属纳米催化剂的精准设计开辟了新途径。
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产品关联
DOI
高影响因子
FUEL
·
2026
·
IF 7.8
Chunyan Tu,Ruonan Pan,Luhan Liu,Hao Wang,Wenlin Li
A novel defect-engineered strategy was developed to fabricate highly efficient Pd catalysts for the selective hydrogenation of phenol to cyclohexanone. By fine-tuning the post-alkali treatment, we successfully tailored the microstructure of halloysite nanotubes (HNTs) supports, selectively removing Al–OH sites without forming any amorphous structures. This precise engineering allowed for the uniform dispersion of ultrafine Pd nanoparticles within the HNTs’ lumen. A comprehensive analysis using CO-DRIFTS, TEM, H 2 -TPD, CO 2 -TPD, and Py-IR techniques revealed that the Pd/1.2M-HNTs catalyst possessed rich Pd step sites with a strong H 2 dissociation ability. Furthermore, the unique acid–base properties of the modified HNTs support moderate the adsorption strength of cyclohexanone, ensuring high selectivity by promoting its timely desorption and limiting over-hydrogenation. The optimized catalyst exhibited superior catalytic performance with a high turnover frequency (TOF) of 341 h −1 and excellent stability. This work highlights a facile and effective approach to control the support structure at the molecular level, offering new insights for the rational design of catalysts for hydrogenation reactions.
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产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2020
·Vol. 55
·期 27
·12876-12883
·
IF 3.553
Zhang Peng,Zhang Hongwei,Wang Shuhan,Lei Xueqin,Yang Jiangtao,Li Zimeng,Zhu Haibo,Bao Xiaojun,Yuan Pei
Silica hollow microspheres with moonscape-like rough surface (RS) and macroporous surface (MS) have been controllably synthesized by a water–oil–water three-phase emulsion method, which are used as supports of the heterogeneous catalysts for the catalytic hydrogenation of nitrile-butadiene rubber (NBR). It is found that Pd can be uniformly dispersed on both amino-functionalized RS and MS supports and both the catalysts show high hydrogenation activity with 100% selectivity to C=C bonds. However, the reusability of Pd/N-RS is much better than that of Pd/N-MS, maintaining 92% of activity without any regeneration treatment after five times of recycling experiment. The high activity retention is because the moonscape-like surface of the RS support is favorable for the contact of NBR macromolecules with the active sites, and more importantly, the NBR macromolecules do not need to diffuse into the interior of the catalyst, leading to fast desorption of the hydrogenated NBR from the surface of catalyst and re-exposure of the active sites.
研究领域:
材料科学
·
催化化学
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DOI
高影响因子
Molecular Catalysis
·
2018
·
IF 0
Ke Li,Ke Liu,Hong Ni,Bin Guan,Reggie Zhan,Zhen Huang,He Lin
A novel catalytic system combining oxidation catalyst with electric field was applied for low-temperature CH 4 oxidation at low CH 4 concentration (0.2% CH 4 ). Compared with conventional catalytic process, significant improvement in activity was observed over PdCeZrO x catalyst in electric field. For example, the light-off temperature (T 50 ) of CH 4 (0.2% CH 4 ) of 1 wt % PdCe 0.75 Zr 0.25 O x catalyst was approximately 255 °C in an electric field with 3 mA electric current. The impact of electric field in CH 4 oxidation over PdCeZrO x catalyst was thoroughly investigated. The XRD and XPS results revealed that electric field provided free electrons that facilitated the release of lattice oxygen in the ceria-zirconia solid solution, therefore reinforced Pd0 oxidation and the formation of palladium oxide (PdO x , x > 0) on catalyst surface. Electric field also enhanced the reducibility of the PdO x , which provided active oxygen for CH 4 oxidation at low temperature. With in-situ FTIR technique, it was found that electric field greatly promotes the chemisorption and dehydrogenation of CH 4 , thereby accelerates the chemical reactions of the intermediate products, so as to promotes CH 4 oxidation. The mechanism of catalytic oxidation of CH 4 in electric field was proposed based on comprehensive investigations above.
研究领域:
催化化学
·
环境科学
·
材料化学
·
能源化学
·
表面科学
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DOI
Nano Research
·
2016
·Vol. 9
·期 6
·1590-1599
·
IF 8.893
Liu Dong,Xie Maolin,Wang Chengming,Liao Lingwen,Qiu Lu,Ma Jun,Huang Hao,Long Ran,Jiang Jun,Xiong Yujie
Formic acid oxidation is an important electrocatalytic reaction in protonexchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCOO* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/activation towards improved electrocatalytic performance.
研究领域:
材料科学
·
电催化
·
纳米技术
·
能量转换
✓ 已验证
DOI
高影响因子
Applied Catalysis O: Open
·
2024
·
IF 0
Kaiyang Xu,Lingfeng Weng,Lizhi Wu,Li Tan,Yu Tang
Cyclohexanone is a key raw material for manufacturing nylon and other chemicals. The sustainable conversion of biomass-derived phenol to cyclohexanone meets the requirements of sustainable development goal but still be challenging. Herein, a catalyst containing isolated Pd cations in zeolite, namely Pd 1 /ZSM-5, is investigated for the partial hydrogenation of phenol to cyclohexanone. Under 140 °C and 1.5 MPa of initial hydrogen pressure, the conversion of phenol reaches 95.6% with the selectivity to cyclohexanone of 99.9%. Besides, the turnover rate (TOR) of partial hydrogenation of phenol reaches 382.7 h −1 . The mild adsorption affinity of cyclohexanone on catalytic sites leads to the high selectivity. Moreover, as unveiled by surface reactivity of phenol monitored by in-situ infrared spectrum, the oxygen atom of phenol hydroxyl group is adsorbed on the Brönsted acid site of Pd 1 /ZSM-5 as the key reaction step. The reaction intermediate involves the partial hydrogenation of benzene ring of phenol.
研究领域:
催化化学
·
绿色化学
·
可持续发展
·
生物质转化
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DOI
危险品化学品经营许可证（带存储）