CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Zhiheng Wang,Jiali Huang,Guancong Jiang,Tuo Ji,Han Lin,Liwen Mu,Xiaohua Lu,Jiahua Zhu
In heterogeneous reactions, catalyst support plays an important role in tuning catalytic activity of metallic structures and regulating fluid transport during reaction, while it needs to be engineered to balance reaction and diffusion for optimized outcome. In this work, a combined delignification and activation strategy was used to prepare a series of carbon supports with varied porous structures and surface properties. Pd was then loaded on the carbon supports for direct synthesis of H 2 O 2 (DSHP) reaction. Results indicated that highly developed meso-macropore structures significantly promoted the dispersion of Pd and exposed more active sites for H 2 dissociation. However, the enrichment of pore structure brought excessive surface oxygen groups, leading to the transition of Pd from Pd 0 to PdO and thus inhibiting the hydrogenation activity. The optimized catalyst, with desirable porous structure and appropriate Pd 0 /PdO ratio, exhibited an extraordinarily high H 2 O 2 productivity of 37346.42 mmol g Pd −1 h −1 under atmospheric conditions. This work provided a case study on the regulation of reactivity and diffusion through catalyst support engineering, demonstrating the essential role of matched reaction–diffusion in heterogeneous DSHP reactions.
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
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Ying Gao,Qinqin Chen,Xinhao Shen,Shuang Yao,Zhiwen Jiang,Sanjian Ma,Hailiang Yang,Juanhong Li,Zixia Lin,Xin Liu
Both the sluggish kinetics of Fe(II) regeneration and usage restriction of H2O2 have severely hindered the scientific progress of the Fenton reaction toward practical applications. Herein, a reduction strategy of activated hydrogen, which was used to simultaneously generate H2O2 and accelerate the regeneration of ferrous in a Fenton-like reaction based on the reduction of activated hydrogen derived from H2, was proposed. Two types of composite catalysts, namely, Pd/UiO-66(Zr)-2OH and Pd@UiO-66(Zr)-2OH, were successfully prepared by loading nano-Pd particles onto the outer and inner pores of UiO-66(Zr)-2OH in different loading modes, respectively. They were used to enhance the reduction of activated hydrogen. The characterization results based on the analysis of scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy revealed that the materials were successfully prepared. By using a trace amount of ferrous iron and without adding H2O2, trimethoprim (C0 = 20 mg·L–1), as a target pollutant, could be nearly 100% degraded within 180 min in the reaction system composed of these two materials. The cycle of iron and the self-generation of H2O2 were verified by the detection of ferrous H2O2 in the system. Density functional theory calculation results further confirmed that the pore-filled Pd0 NPs, as the main catalytic site for Pd@UiO-66(Zr)-2OH, could produce H2O2 under the combined action of hydrogen and oxygen. The Pd@UiO-66(Zr)-2OH system had excellent stability after multiple applications (at least 6 cycles), all of which resulted in 100% removal of trimethoprim. The degradation efficiency of the Pd/UiO-66(Zr)-2OH system for TMP gradually decreased from 97 to 80% after six cycles. The results of electron paramagnetic resonance combined with classical radical burst experiments revealed the degradation pathways in the reaction system with hydroxyl radicals and singlet oxygen as the main reactive oxygen particles.
研究领域:
环境科学
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催化化学
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DOI
PubMed
高影响因子
Molecular Catalysis
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2023
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IF 4.6
Minghao Zha,Hao Yan,Ruiying Li,Yinghao Sun,Ruitong Wang,Yibin Liu,Xiaobo Chen,Xin Zhou,Xiang Feng,Chaohe Yang
Reducing the formation of trans fatty acid in vegetable oil hydrogenation process is of significance to ensure food safety. Herein, Pd 0 -O 2− -Ce 3+ active site was constructed by strong electronic interactions between Pd 0 and CeO 2 -Polyhedrons to promote the formation of cis fatty acid. Results reveal that the abundant oxygen vacancies of CeO 2 (111) facets promote the adsorption and activation of hydrogen, leading to excellent catalytic activity of Pd/CeO 2 -Polyhedrons. Moreover, electronic reconstructed Pd 0 -O 2− -Ce 3+ active site limits the σ-bond rotation of half-hydrogenated intermediates through enhancing π backdonation and weakening the σ-bond, contributing to the reduction of trans products. Under mild conditions (30 °C, 0.3 MPa H 2 , and 2 h), Pd/CeO 2 -Polyhedrons catalyst shows exceptional methyl oleate selectivity of 52.6% with 93.8% conversion for sunflower oil hydrogenation. The catalyst has been further extended to the selective hydrogenation to several other vegetable oils such as sunflower oil, peanut oil, soybean oil, among others, under mild conditions.
研究领域:
催化化学
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食品安全
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材料科学
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DOI
高影响因子
RSC Advances
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2020
·Vol. 10
·期 70
·43175-43186
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IF 3.119
Jinqiang Tan,Huamei Zhu,Shasha Cao,Sisi Chen,Yuanfu Tian,Dachuan Ding,Xuan Zheng,Chuanqun Hu,Tao Hu,Chonggang Wu
A poly(methyl methacrylate)-supported Pd0 nanocatalyst was successfully prepared from solution reaction of Pd(CH3COO)2 with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA–MAA). The reaction was carried out in a benzene/methanol mixed solvent in the dark at room temperature (∼25 °C) in the absence of a typical chemical reductant. There was coordination between the Pd0 nanoclusters and MMA–MAA, resulting in Pd0 nanoclusters being stably and uniformly dispersed in the MMA–MAA matrix, with an average particle size of ∼2.5 ± 0.5 nm. Mechanistically, it can tentatively be proposed that PMMA-ionomerization of the Pd2+ ions produces intramolecular –2COO−–Pd2+ aggregate cross-links in the solution. On swelling of the chain-segments that are covalently bound via multiple C–C bonds, the resultant elastic forces cause instantaneous dissociation at the O–Pd coordination bonds to give transient bare (i.e., uncoordinated), highly-oxidative Pd2+ ions and H+-associative carboxylate groups, both of which rapidly scavenge electrons and protons, respectively, of the active α-H atoms abstracted from the methanol molecules of the solvent to make Pd0 nanoclusters supported by the re-formed MMA–MAA. The MMA–MAA acid copolymer, without itself undergoing any permanent chemical change, serves as a mechanical activator or catalyst for the mechanochemical reduction of Pd(CH3COO)2 under mild conditions. Compared with traditional Pd/C catalysts, this Pd0 nanocatalyst exhibited more excellent catalytic efficiency and reusability in the Heck reaction between iodobenzene and styrene, and it could be easily separated. The supported Pd0 nanocatalyst prepared using this novel and simple preparation method may display high-efficiency catalytic properties for other cross coupling reactions.
研究领域:
材料科学
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催化化学
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PubMed
高影响因子
Catalysis Science & Technology
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2018
·Vol. 8
·期 7
·1858-1866
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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
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环境科学
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DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2025
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IF 11.3
Jian Gao,Yuqi Shi,Minglu Tang,Yuancai Chen
Chromate bioreduction is a promising bioremediation strategy, but its application in wastewater treatment is limited by the Cr(VI) biotoxicity, particularly due to the generation of Cr(VI)-induced reactive oxygen species (ROS). To mitigate these adverse effect, this study synthesized bio-Pd 0 in Citrobacter freundii to modulate distinct Cr(VI) aerobic/anaerobic reduction pathways. With the incorporation of bio-Pd 0 , aerobic and anaerobic Cr(VI) specific removal rate increased by 18.1–21.2 and 51.5–87.9 times, respectively. The genomics, RT-qPCR, respiratory inhibition experiments, ROS levels and antioxidant enzyme activity assays demonstrated that bio-Pd 0 enhanced intracellular Cr(VI) aerobic bioreduction mainly via upregulating the chromate multi-electron reductase (Cr-MER) (related with YieF, NfsA and NemA), together with the energy-dependent resistance system (antioxidant enzyme superoxide dismutase and catalase, efflux pump Emr, DNA repair protein RecG). Cr-MER and resistance system effectively reduced the generation and accumulation of ROS, respectively. For anaerobic conditions, bio-Pd 0 facilitated hydrogenase-mediated short respiratory chain (S-chain) to reduce Cr(VI) extracellularly (related with HypE, RutF and OmcG), avoiding ROS generation and the energy consumption of the intracellular detoxification system, and maximized the energy utilization for Cr(VI) extracellular reduction. This study provides a new strategy for Cr(VI) bioreduction and elucidates the underlying mechanism.
研究领域:
环境生物技术
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微生物学
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生物修复
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生物化学
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基因组学
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毒理学
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DOI
PubMed
高影响因子
Journal of Cleaner Production
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2024
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IF 9.7
Linya Yi,Shuyan Chen,Yuancai Chen
Bio-remediation are low-cost and environmentally friendly, but microbial enzymes tend to lose their activity when treated antibiotic contaminants due to its high toxicity. In this study, Bacillus megaterium Y-4 was demonstrated to in situ synthesize Pd 0 @cells, and detoxify oxytetracycline (OTC) through enhancing electron transport chain via Pd 0 -dependent F O F 1 -ATPase (proton pumps). Toxicity analyses showed that increasing Pd 0 loading significantly reduced acute and chronic bio-toxicity as well as ecological risk of OTC effluent, as evidenced by the promoting cellular response to oxidative stress with increasing enzymes GSH-Px and IDH activities (4.24 and 1.20-fold). Electrochemical (I-t, LSV, DPV and EDC) showed that the incorporated bio-Pd 0 mainly promoted FDH/Hase-based short chain (gradually took precedence over CoQ-based long chain), diverting OTC extracellular degradation to markedly detoxify OTC to cell. Inhibition (DCCD and TBA) assays and structural equation modelling indicated that bio-Pd 0 upregulated ATP and NADH synthesis. It also acted as transmembrane F O F 1 -ATPase proton pump, which enabled the backward of protons out of the restriction of PMF , eventually maximizing the energy utilization. This study sheds new insights into the detoxification of antibiotics by bio-nanoparticles through proton transmembrane transfer/redistribution.
研究领域:
微生物学
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环境科学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2026
·
IF 7.6
Yinheng Zhao,Jiaqi Li,Yuyun Xie,Yiwei Yang,Zhenggang Xu,Chenggen Li,Yingjie Ding,Ting Zhu,Yuan Dong,Hansong Cheng,Ming Yang
To overcome the activity and durability bottlenecks of Pd catalysts in the deep dehydrogenation of liquid organic hydrogen carriers (LOHCs), we couple dielectric-barrier cold plasma with CeO2 modulation. This green, low-energy cold-plasma process treats a Ce-doped Pd/C precursor at near-room temperature, redistributing the oxide and constructing a stable CeO2-carbon (CeO2–C) interface, and drives Pd nanoparticles to anchor at this interface, generating electron-deficient Pdδ+ sites in intimate contact with Pd0. Structure-performance correlations show that the new interface greatly increases Pd dispersion and Lewis-acid site density, while the Pdδ+ centers, through concurrent electronic withdrawal and acidity enhancement, accelerate the rate-determining 4H-NPCZ → NPCZ step. Consequently, with a catalyst mass fraction of 20 wt %, PdCe5C–Ar achieves complete dehydrogenation of fully hydrogenated N-propylcarbazole (12H-NPCZ) within 240 min at 180 °C and delivers a mass-specific hydrogen-release rate of 223.0 mmol H2 gmetal–1 min–1─almost twice the best literature value─while retaining full activity after eight cycles. DFT calculations attribute the performance leap to a downward shift of the Pd d-band center and to a lowered third-step barrier (ΔH3 = 2.381 eV) induced by Pdδ+. This work is the first to apply low-temperature plasma interface engineering to a Pd-CeO2–C ternary system, offering a broadly applicable paradigm for low-Pd, high-efficiency, long-life LOHC dehydrogenation catalysts.
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2026
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IF 9.6
Yinying Shu,Songqi Li,Yuquan Li,Cheng Zheng,Xiaogang Yang,Yahui Cai,Zhengying Wu,Jundie Hu,Jiafu Qu
Interfacial engineering enables Pd 0 /oxygen vacancy balance in Pd/In 2 O 3 . • Hollow In 2 O 3 nanotubes moderate Pd-In 2 O 3 metal-support interaction. • Pd/h-In 2 O 3 achieves 8020 mmol FA mol Pd −1 h −1 for formate production. • Pd 0 retention and defect accessibility jointly govern formate formation. The catalytic performance of oxide-supported Pd catalysts in CO 2 hydrogenation is highly dependent on the interfacial cooperation between metallic Pd 0 sites and defect-containing oxide domains. However, how to regulate this metal-oxide interfacial balance to simultaneously promote H 2 activation and CO 2 -derived intermediate conversion remains insufficiently understood. Herein, we develop an interfacial engineering strategy to regulate the balance between metallic Pd 0 sites and oxygen vacancies (Ov) in Pd/In 2 O 3 catalysts through morphology-dependent metal-support interaction (MSI). Structural analyses reveal that hollow In 2 O 3 nanotubes (h-In 2 O 3 ) effectively moderate Pd-In 2 O 3 interactions, preserve a higher fraction of metallic Pd 0 , and maintain accessible defect-associated oxide domains, thereby establishing a more favorable interfacial configuration than compact counterparts. Consequently, Pd/h-In 2 O 3 delivers the highest formate production rate of 8178 ± 145 mmol FA mol Pd −1 h −1 at 60 °C and 2 MPa, representing a sixfold enhancement over rod-like Pd/In 2 O 3 (Pd/r-In 2 O 3 ), together with excellent stability. These findings highlight that the coordinated regulation of metallic-site preservation and defect accessibility is critical for constructing efficient metal-oxide interfaces for CO 2 hydrogenation to formate. Interfacial engineering optimizes the Pd 0 /Ov balance in Pd/In 2 O 3 by moderating metal-support interaction, enabling high formate productivity (8178 ± 145 mmol FA mol Pd −1 h −1 ) in CO 2 hydrogenation. Download: Download high-res image (147KB) Download: Download full-size image
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高影响因子
TRANSACTIONS OF TIANJIN UNIVERSITY
·
2024
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IF 6.7
Meng Zhaohui,Liao Ying,Liu Ling,Li Yaqian,Yan Hao,Feng Xiang,Chen Xiaobo,Liu Yibin,Yang Chaohe
Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups (e.g., C=C and C=O) is a promising yet challenging endeavor. In our study, we developed a Pd/CeO 2 catalyst by enhancing the oxygen vacancy (O V ) concentration in CeO 2 through high-temperature treatment. This process led to the formation of an interface structure ideal for supporting the hydrogenation of methyl oleate to methyl stearate. Specifically, metal Pd 0 atoms bonded to the O V in defective CeO 2 formed Pd 0 –O V –Ce 3+ interfacial sites, enabling strong electron transfer from CeO 2 to Pd. The interfacial sites exhibit a synergistic adsorption effect on the reaction substrate. Pd 0 sites promote the adsorption and activation of C=C bonds, while O V preferably adsorbs C=O bonds, mitigating competition with C=C bonds for Pd 0 adsorption sites. This synergy ensures rapid C=C bond activation and accelerates the attack of active H* species on the semi-hydrogenated intermediate. As a result, our Pd/CeO 2 -500 catalyst, enriched with Pd 0 –O V –Ce 3+ interfacial sites, demonstrated excellent hydrogenation activity at just 30 °C. The catalyst achieved a Cis–C18:1 conversion rate of 99.8% and a methyl stearate formation rate of 5.7 mol/(h·g metal ). This work revealed the interfacial sites for enhanced hydrogenation reactions and provided ideas for designing highly active hydrogenation catalysts.
研究领域:
催化化学
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材料科学
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高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2026
·
IF 5.4
Jiarui Lu,Yi Yang,Yajing Duan,Chen Wang,Minzhe He,Jinglong Pan,Ling Zhu,Cunzhen Liang,Lian Yu
Pd nanoparticles and oxygen vacancies were co-constructed onto anatase TiO 2 . • Pd-TiO 2-x achieved 98.62% toluene removal and 84.3% mineralization. • Pd sites promoted electron transfer while oxygen vacancies activated O 2 . • Interfacial coupling enhanced reactive charge utilization and ROS generation. • Pd-TiO 2-x retained over 98% toluene removal after five cycles. The efficient photocatalytic removal of gaseous toluene over TiO 2 is hindered by rapid charge-carrier recombination, inefficient interfacial charge utilization, and limited surface oxygen activation. In this study, Pd nanoparticles and oxygen-vacancy-related defects were simultaneously introduced onto anatase TiO 2 through a one-step NaBH 4 reduction strategy. Pd, TiO 2 , TiO 2-x , and Pd-TiO 2-x were examined to distinguish the respective roles of Pd sites, defect-associated sites, and their coupled interface. Pd-TiO 2-x exhibited an actual Pd loading of 0.948 wt%, with Pd predominantly present in metallic Pd 0 state. Compared with TiO 2-x , Pd-TiO 2-x exhibited a higher concentration of oxygen vacancies and a lower interfacial charge-transfer resistance. Under UV light irradiation, Pd-TiO 2-x achieved a toluene degradation efficiency of 98.62% and a mineralization efficiency of 84.30% after 120 min, with an apparent pseudo-first-order rate constant of 0.06282 min −1 . Notably, despite exhibiting the lowest transient photocurrent among TiO 2 -based catalysts, Pd-TiO 2-x showed the highest photocatalytic activity. This non-parallel behavior suggested that its performance advantage arose primarily from the preferential interfacial migration and reactive utilization of photogenerated charge carriers, rather than from an increase in measurable charge output. Mechanistic analyses indicated that Pd 0 -rich sites promoted electron acceptance and transfer, whereas oxygen-vacancy-related sites facilitated O 2 adsorption and activation, thereby promoting the formation of • O 2 ⁻ and • OH. These results highlighted the reactive utilization of interfacial charges as an important factor governing toluene photocatalytic oxidation. Download: Download high-res image (153KB) Download: Download full-size image
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高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Xin Song,Fangjun Shao,Zijiang Zhao,Xiaonian Li,Zhongzhe Wei,Jianguo Wang
Precise regulation of reaction selectivity at high conversions is the key to non-terminated alkyne semi-hydrogenation. Herein, a support modification strategy was employed to incorporate trace amounts of Mg elements into alumina support. The modified support loaded Pd catalyst optimized the activity and selectivity of the non-terminated alkyne semi-hydrogenation reaction. The TEM and XRD characterization of the catalysts demonstrated the entry of Mg elements into the Al 2 O 3 lattice to achieve the modification of the support. For the 2-butyne-1-ol semi-hydrogenation reaction, the Pd 0.5 /Mg 1 @Al 2 O 3 catalyst showed 99 % conversion and 97 % selectivity of the cis product at hydrogen pressure of 0.1 MPa and 25 °C. The introduced Mg element changed the electronic structure of Pd nanoparticles in the catalyst. The precise regulation of the 2-butyne-1-ol semi-hydrogenation reaction was achieved by adjusting the ratio of Pd 0 to Pd 2+ using the synergistic effect of Pd 0 and Pd 2+ .
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
危险品化学品经营许可证（带存储）