RENEWABLE ENERGY
·
2022
·
IF 8.634
Siteng Rong,Hongzi Tan,Zhaobin Pang,Zhiyuan Zong,Rongrong Zhao,Zhihe Li,Zhe-Ning Chen,Ning-Ning Zhang,Weiming Yi,Hongyou Cui
Lignin could be depolymerized into large amount of phenolic compounds via fast pyrolysis . The upgrade of phenolic compounds via hydrodeoxygenation (HDO) involves multiple reaction pathways. It is challenging to selectively remove the oxygen-containing groups while keeping the aromatic rings intact. In this work, hierarchical Nb 2 O 5 (H–Nb 2 O 5 ) microspheres with abundant oxygen vacancies were synthesized to anchor the Pd clusters, which is featured with strong metal-support interaction via the electron transfer between Pd species and Nb species. For phenol HDO reaction, the oxygen vacancies were prone to interact with the phenolic hydroxy groups, resulting in phenol molecule adsorbed in a “nonplanar” manner, greatly weakening the C Ar -O bonds and averting the ring hydrogenation. Besides, the activated hydrogen atoms on Pd clusters could migrate to the vicinity of oxygen vacancies via spillover, promoting the cleavage of C Ar -O bond to obtain benzene. Current work provides a deep insight into the synergetic catalytic mechanism of Pd/H–Nb 2 O 5 catalyst for phenol HDO reaction, and also sheds light on the design and synthesis of high-efficient catalysts in other heterogeneous catalysis fields.
研究领域:
催化化学
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材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2020
·
IF 3.687
Qian Wang,Meiling Ge,Yuheng Dou,Fu Yang,Junkai Wang,Yuyang Shao,Agen Huang
Polymer supports play an important role in noble metal loaded catalysts. In this study, palladium clusters stabilized by several polyamides have been widely studied in the oxidation of benzyl alcohol under airflow. The different kinds of polyamides (PADs) were synthesized with aromatic diamines and trimesoyl chloride by mechanical grinding method and solvent-heat method. Polyamide support was synthesized through mechanical grinding method. And the laminar structure and abundant amide bonds of polyamide can help obtain ultrafine Pd clusters with a mean particle size of 1.76 nm. The Pd 0.5 @PAD-2-M effectively catalyzed benzyl alcohol into benzaldehyde with a conversion of 96.1 % and turnover number (TON) of 1441 under 90 °C in water which was 2.5 times higher than the commercial Pd/C catalyst. High TON value of 6505 was also achieved in solvent-free system. This work reveals the advantages of laminar structure of polyamide in dispersing Pd clusters and promoting benzyl alcohol conversion. Besides, the carrier properties of amphipathy and substrate adsorption were also investigated to illustrate the significance of interfacial effect for laminar catalyst in heterogeneous catalysis.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY
·
2022
·
IF 7.129
Shihuan Lu,Xizi Li,Bingzhi Yu,Jiafeng Ding,Yuchi Zhong,Hangjun Zhang
Efficient treatment of cyanobacterial blooms in eutrophication waters by safe and reliable nanomaterials is a big challenge for reducing environmental health risks. Herein, a novel strategy combining palladium clusters (Pd n ) with g-C 3 N 4 nanocomposite was presented to achieve high-efficient removal of Microcystis aeruginosa cells through coagulation and breakage. Interestingly, 95.17% of algal cells (initial concentration of 5.6 × 10 6 cells mL −1 ) were promptly removed in the Pd/g-C 3 N 4 (5%) system within only 10 min and without visible light irradiation and persulfate activation. Both the release of potassium ion and microcystin during the removal process and the transmission electron microscope observations of Microcystis aeruginosa cells proved that the integrity of the algal cell membrane was destroyed. The removal of Microcystin-LR (MC-LR) were further confirmed in the next process. Pd metal interaction and breakage against algal cells may cause disruption of algal cells. This study describes a novel technology for the superfast removal of harmful algae and may provide a new insight into the control of cyanobacterial blooms in practical applications.
研究领域:
环境科学
·
微生物学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Lei Wang,Badusha Mohamad Ali,Siyang Yu,Sheng Liang,Qingqing Huang,Hao Zhang,Lingyu Zhu,Jianli Wang
Pickering interfacial catalysts incorporated with amphiphilic architecture significantly expand the sustainability of green catalysis systems. In this work, we present precise and well-designed dumbbell-shaped Janus-structured polymeric nanoparticles with one-side anchored palladium clusters (DB-JPP-Pd) as Pickering interfacial catalyst for static hydrogenations. The large wettability difference of each lobe renders the prominent amphiphilicity of the dumbbell-shaped DB-JPP-Pd. The amphiphilic Janus catalyst displays excellent interfacial activity and extensively reduces the interfacial tension from 34.06 ± 0.13 to 20.54 ± 0.31 mN/m, promoting the formation of a more stable Pickering emulsion than that of the bulk PS-Pd catalyst, which can continuously provide a large interfacial area and shorten the molecular mass transfer distance during the reaction process. As a result, the DB-JPP-Pd catalyzed nitroarene reduction reaction exhibits a normalized reaction rate constant (k nor ) of 3.39 min −1 ⋅g −1 ⋅L under static conditions, which is 56.5 times higher than that of bulk PS-Pd. The constructed Pickering interfacial catalysis (PIC) system converts all the nitrobenzene into aniline within three minutes and possesses excellent selectivity in hydrogenations of different nitro aromatics. In addition, the emulsion catalytic system was conveniently recycled for ten consecutive runs. Hence, this unique amphiphilic dumbbell-shaped catalyst effectively develops an efficient static biphasic catalysis system.
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2024
·
IF 4.8
Hongyan Wang,Xinyue Sun,Jingpei Cao,Yajie Tian,Bofeng Zhang
Zeolite catalysts have been widely applied in petroleum and chemical industries. Nano/hierarchical structure could improve the utilization efficiency of active sites, especially for metal species encapsulated in zeolites. However, the uniformity of zeolite surface and crystallinity would decrease, leading to low stabilization effect. Herein, we developed a seed-directed method to prepare Pd clusters (∼1.3 nm) regioselectively encapsulated in hollow polycrystalline shell of Silicalite-1 zeolite. In nitrobenzene hydrogenation reaction, the optimized Pd@S-1-hp showed a high conversion of 92.2 % at 110 °C, which is 40 % higher than that of Pd clusters in bulk zeolite. Sub-nano Pd species in polycrystalline shell could significantly shorten the diffusion length on the basis of strong microporous confinement effect. Catalytic hydrogenation activity remained stable after six cycles. This structure could be extended to heterogeneous reactions suffering from diffusion limitation.
研究领域:
化学工程
·
催化材料
✓ 已验证
DOI
高影响因子
Frontiers in Chemistry
·
2022
·
IF 5.545
Liu Yangqing,Sun Jingwen,Fan Lan,Xu Qi
Subnanometer noble metal clusters have attracted much attention because of abundant low-coordinated metal atoms that perform excellent catalytic activity in various catalytic processes. However, the surface free energy of metals increases significantly with decreasing size of the metal clusters, which accelerates the aggregation of small clusters. In this work, new Schiff base–imidazole-functionalized MOFs were successfully synthesized via the postsynthetic modification method. Highly dispersed Pd clusters with an average size of 1.5 nm were constructed on this functional MOFs and behaved excellent catalytic activity in the Suzuki coupling of phenyboronic acid and bromobenzene (yield of biaryl >99%) under mild reaction conditions. Moreover, the catalyst can be reused six times without loss of activity. Such catalytic behavior is found to closely related to the surface functional groups that promote the formation of small Pd0 clusters in the metallic state.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano Research
·
2021
·Vol. 14
·期 7
·2441-2450
·
IF 8.897
Peng Lingxin,Tian Han,Cui Xiangzhi,Su Liang,Meng Ge,Ma Zhonghua,Cao Shaowen,Shi Jianlin
Developing anode catalysts of substantially enhanced activity for hydrogen oxidation reaction (HOR) and anti-CO poisoning performance is of great importance for the application of proton exchange membrane fuel cells (PEMFCs). Herein, we report Pd cluster in situ decorated urchin-like W 18 O 49 (WO 2.72 ) electrocatalysts by a photo-reduction method for high performance HOR. The synthesized Pd-WO 2.72 -L composite of low loading amount of 0.44 wt.% Pd by Xenon light reduction exhibits markedly high HOR catalytic activity and stability in 0.5 M H 2 SO 4 , and the specific HOR current density and mass activity of Pd-WO 2.72 -L are ∼ 1.5 and ∼ 80 times those of 20 wt.% Pt/C catalyst, respectively. Moreover, excellent anti-CO poisoning ability has also been obtained. The excellent HOR activity and anti-CO poisoning performance of Pd-WO 2.72 -L have been discussed mainly in terms of the dual synergetic catalytic effects between Pd and WO 2.72 : Pd activation to Pd δ+ by the electron transfer from Pd to W promotes the hydrogen adsorption and activation to H* species, which results in largely elevated HOR activity; Pd degradation due to the CO poisoning is effectively prevented by WO 2.72 , which is responsible for the excellent CO-tolerance performance.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Xiao-Chen Ma,Chun Pu,Yue-Xing Zhang,Gang-Gang Chang,Ge Tian,Si-Ming Wu,Jia-Wen Liu,Zhi-Yi Hu,Li-Ying Wang,Yi-Xia Yin,Christoph Janiak,Xiao-Yu Yang
Efficient regeneration of Pd catalysts is a challenge and has a very high technological importance. Herein, we report confined Pd clusters with the ultrafine size (1.2 nm) and ultralow loading amount (0.14 wt%) in a metal–organic framework (MOF), which could potentially allow for the successive realization of the cascade-type catalytic reaction from starting reagents to final desired products, and thus to avoid the excessive processes, save energy and reduce waste. Experiments and theoretical computations have been conducted to study the strong host–guest interaction between the Pd clusters and the MOF support, leading to the high catalytic activity and dynamic of the Pd clusters. A unique dynamic structure from active disordered arrangement to deactive crystalline arrangement and then back to the active disordered arrangement (>99% of activity after regeneration by simple H 2 reduction). The MOF-confined Pd shows excellent catalytic activity (>99% activity), selectivity (around 100%) and stability (>99% activity after recycling) under mild reaction conditions (atmospheric temperature and pressure).
研究领域:
催化
·
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2024
·
IF 4.4
Yulu Chen,Hongyan Pan,Chunliang Yang,Haipeng Xiao,Zheng Chen,Chun Zhu,Weiyue Zhao,Qian Lin
Direct synthesis of hydrogen peroxide (H2O2) by hydrogen and oxygen is an atom-efficient and environmentally benign method. However, achieving high H2O2 selectivity and productivity with sub-nanometer Pd clusters remains challenging due to the tendency of undercoordinated surface sites to cleave O-O bonds and form water. Herein, sub-nanometer Pd clusters are confined to ammonia-treated ZIF-8-derived mesoporous carbon (ZDC) with controlled nitrogen configurations, which facilitates the effective direct synthesis of H2O2 by optimizing the electronic structure of Pd atoms via strong metal-support interaction (SMSI). The sub-nanometer catalyst Pd/ZDC1.0 achieves a remarkable H2O2 selectivity of 81.6% and productivity of 3317 mmol/gPd•h-1, which is 12.5% and 123.1% higher than the sub-nanometer catalyst Pd/XC-72 without nitrogen doping, respectively. Structural characterization shows that the pore structure and pyridine nitrogen content of Pd/ ZDCX are proportional to the ammonia-treated time. Theoretical calculations demonstrate that there is a strong electron transfer between sub-nanometer Pd clusters and pyridine nitrogen sites, leading to a downward shift in the d-band center of Pd atoms. The electronic effect weakens the adsorption of reactive intermediates on undercoordinated surface sites and suppresses O-O bond dissociation, contributing to enhanced selectivity and preventing water formation
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Kai-Qiang Jing,Yu-Qing Fu,Zhe-Ning Chen,Teng Zhang,Jing Sun,Zhong-Ning Xu,Guo-Cong Guo
Strong metal–support interaction is crucial to the stability of catalysts in heterogeneous catalysis. However, reports on boosting interfacial electron transfer between metal and support via defect induction for enhanced metal–support interaction are limited. In this work, ultrathin reducible ZnTi-layered double hydroxide (LDH) nanosheets with rich oxygen defects were synthesized to stabilize Pd clusters, and the rich oxygen defects promoted Pd cluster bonding with Zn and Ti atoms in supports, thereby forming a metal–metal bond. Electron spin resonance (ESR), X-ray absorption fine spectra (XAFS), and density functional theory (DFT) calculations demonstrate remarkable interfacial electron transfer (0.62 e). The Pd/ZnTi-LDH catalyst shows superior catalytic stability for CO direct esterification to dimethyl oxalate. By contrast, the nonreducible Pd/ZnAl-LDH catalyst with a few oxygen defects shows minimal interfacial electron transfer (0.08 e), which leads to relatively poor catalytic stability. This work provides a deep insight into promoting the stability of catalysts by boosting interfacial electron transfer via defect induction.
研究领域:
催化化学
·
材料科学
·
理论计算
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2024
·
IF 11.2
Guilin Wei,Junhong Luo,Wenwen Yong,Jiangfeng Song,Yan Shi,Xingwen Feng,Ning Liu
Controllable nuclear fusion is a major breakthrough in the future energy field and an important way for mankind to pursue clean and sustainable energy. However, since the fusion reaction raw material tritium is radioactive (β decay, half-life is 12.43 years), the leakage of these hydrogen isotopes under accident conditions will bring the risk of explosion and cause radiation damage to human. Therefore, efficient removal of hydrogen isotopes leaked due to accidents is crucial to the safe operation of nuclear fusion and human health. This study utilizes the metal-support interaction effect to design a series of Pd catalysts for efficient catalytic oxidation of hydrogen isotopes. Using pure silicon zeolite as a carrier, Pd is confined in the channel structure using a ligand-stabilized in situ encapsulation method. The prepared catalyst has nanoscale dispersed metal clusters and has excellent hydrogen isotope catalytic oxidation performance. This study systematically explored the effects of catalyst post-treatment methods, reaction space velocity, and reaction temperature on the hydrogen isotope catalytic oxidation conversion rate. The results show that the catalyst can be fully reduced at 600 °C and can achieve a hydrogen isotope catalytic oxidation conversion rate of greater than 98 % (24,000 mL g –1 h –1 ) at 100 °C. The conversion rate for hydrogen is higher than 96 % under the same space velocity at 50 °C. After 35,360 min (∼24.5 d) of continuous testing and intermittent operation, the catalyst can also maintain a conversion rate of 99 % (100 °C, 24,000 mL g –1 h –1 ). A lower reduction temperature will leave some organic matter, which will coordinate and bond on the Pd clusters and thus affect the catalytic activity. Under the same conditions, the hydrogen conversion rate of the catalyst directly reduced at 400 °C was 14 % lower than that of reduction at 600 °C, which proves the criticality of the reduction temperature. This work demonstrates a systematic study of utilizing the confinement effect of molecular sieve pores to obtain Pd cluster catalysts and applying them to the oxidative removal of hydrogen isotopes. It focuses on exploring the impact of the direct reduction temperature of the catalyst on its performance, which may be useful for providing a certain reference for designing relevant catalysts in engineering applications.
研究领域:
化学工程
·
核能科学
·
催化材料
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-15
·
IF 15.7
Zhao Ke,Tan Liang-Xiao,Gao Ning,Sun Jian-Ke
Combining the chemo- and biocatalytic sites within an integrated catalyst to orchestrate complex, multi-step reactions is highly desirable yet remains a significant challenge. Here, we introduce an ionic organic cage platform for such a chemoenzymatic catalyst, achieved by electrostatic complexation of cationic molecular cage-encapsulated Pd clusters (Pd@C-Cage + ) and anionic Candida antarctica lipase B. The spatial compartmentalization provided by the cage scaffold averts undesirable coordination interactions between metal and enzyme, while also facilitating substrate channelling between dual active sites in the one-pot tandem dynamic kinetic resolution of amines, resulting in 2.1-2.7 folds enhancement in product yield within the same reaction time, compared to the physical mixture of individual analogues, and even one order of magnitude higher than the mixture of commercial immobilized lipase Novozym 435 and Pd/C. Additionally, the well-defined pore aperture and charged cage skeleton enables precise microenvironment engineering of confined metal sites, providing stringent site/shape selectivity towards substrates featuring different substituents and sizes. This platform is further demonstrated by integrating other metal clusters (e.g., Ru) and enzymes (e.g., Candida antarctica lipase A, Thermomyces lanuginosus lipase, and Glucose oxidase) for a variety of chemoenzymatic reactions, with 2.1–5.3 folds enhancement compared to the physical mixture of individual analogues.
研究领域:
催化化学
·
有机化学
·
生物无机化学
·
酶工程
·
纳米技术
·
材料科学
·
化学生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）