CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Qiqi Lu,Xiu-Zhi Wei,Haiyong Wang,Qi zhang,Xinghua Zhang,Lungang Chen,Jianguo Liu,Longlong Ma
The selective hydrogenation of nitrile represents an atom-economical and reliable method to synthesize primary amine, a privileged compound in chemistry, biology, and medicine. However, this approach often displays severe selectivity issues, and additives or reducing agents are generally required to solve this problem. In this work, we aim to synthesize primary amine on a green catalytic system and probe into the catalytic mechanism of Pd-Ni interaction using benzonitrile (BN) as a model compound. The nitrile hydrogenation reaction was catalyzed by bimetallic Pd-Ni oxide nanospecies confined in Silicalite‑1 (S-1) zeolite using H 2 as hydrogen donor without any additive which was environmentally friendly and economic. A 92% yield of benzylamine (BA) was achieved on the [email protected] catalyst with a turnover number (TON) of 1667, and such BA yield was still maintained in upscaling experiment. Detailed characterizations shed light on the mechanism of the extraordinary performance of Pd-Ni oxide nanospecies on base-free nitrile hydrogenation.
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Advanced Science
·
2023
·
IF 15.1
Saijun Wang,Zaigang Zhou,Rui Hu,Mingyue Dong,Xiaobo Zhou,Siyan Ren,Yi Zhang,Chengxun Chen,Ruoyuan Huang,Man Zhu,Wanying Xie,Ling Han,Jianliang Shen,Congying Xie
At present, radiotherapy (RT) still acquires limited success in clinical due to the lessened DNA damage under hypoxia and acquired immune tolerance owing to the amplified programmed death ligand-1 (PD-L1) expression. Incredibly, intracellular PD-L1 expression depression is proven to better sensitize RT by inhibiting DNA damage repair. However, the disability of the clinically used antibodies in disrupting the extracellular PD-L1function still limits the effectiveness of radio-immunotherapy. Therefore, better PD-L1 regulation strategies are still urgently needed to better sensitize radio-immunotherapy. Hence, for this purpose, TPP-LND is synthesized by linking mitochondrial-targeted triphenylphosphine cations (TPP + ) to the antineoplastic agent lonidamine (LND), which significantly reduces the dose needed for LND to induce effective oxidative phosphorylation inhibition (2 vs 300 µ M ). Then, TPP-LND is wrapped with liposomes to form TPP-LND@Lip nanoparticles. By doing this, TPP-LND@Lip nanoparticles can sensitize RT by reversing the hypoxic microenvironment of tumors to generate more DNA damage and reducing the expression of PD-L1 via enhancing the adenosine 5′-monophosphate-activated protein kinase activation. As expected, these well-designed economical TPP-LND@Lip nanoparticles are more effective than conventional anti-PD-L1 antibodies to some extent.
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PubMed
高影响因子
ACS Applied Nano Materials
·
2023
·
IF 5.9
Lulu Kong,DeZhu Chen,Xiaolong Zhang,Lin Zhou,Yongming Deng,Shaohua Wei
The growth of oxides on the surface of noble metals and the introduction of alloys are effective methods to enhance the catalytic activity of noble metals. However, the fabrication of noble metal oxides always involves harsh experimental conditions and the oxidation degree could not be controlled. Herein, a simple, fast, and controlled Pd oxidation method by mixing Hg2+ and Pd nanosheets (PdNSs) under mild conditions to form PdxHgy(PdO)z (PHOs) was reported, which consists of the Pd–Hg alloy and PdO. The density functional theory (DFT) calculation and experiment results proved that the Hg atom incorporation promotes the nearby Pd–Pd bond breaking, initiating a cascade of PdO generation. More precisely, 1 Hg atom incorporation induced ∼8 Pd atom oxidation, ensuring that the oxidation degree of Pd could be easily controlled by adjusting the ratio of Hg2+ and PdNS. As a peroxidase-mimicking nanozyme, the PHO affinity for its substrate could be 21.7- and 123.6-fold greater than that of the PdNS and the natural peroxidase (HRP), respectively. For the colorimetric immunoassay of carcinoembryonic antigen (CEA) detection, PHO has an ultralow detection limit of 1.33 pg mL–1, which is ∼8.6 and ∼282 times lower than that of the PdNS and the natural HRP, respectively.
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Catalysts
·
2023
·Vol. 13
·期 4
·643
·
IF 3.9
Minming Bao,Yuxi Liu,Jiguang Deng,Lin Jing,Zhiquan Hou,Zhiwei Wang,Lu Wei,Xiaohui Yu,Hongxing Dai
The development of efficient and stable catalysts is of great importance for the elimination of volatile organic pollutants (VOCs). In this work, AuPdxnanoparticles (NPs) were loaded on TiO2through the electrostatic adsorption approach to generate theyAuPdx/TiO2(i.e., 0.35AuPd0.46/TiO2, 0.34AuPd2.09/TiO2, and 0.37AuPd2.72/TiO2;xandyare Pd/Au molar ratio and AuPdxloading, respectively;x= 0.46–2.72; andy= 0.34–0.37 wt%) catalysts, and their catalytic activities for the oxidation of ethyl acetate were determined. The results showed that the 0.37AuPd2.72/TiO2sample exhibited the best activity (T50%= 217 °C andT90%= 239 °C at SV = 40,000 mL/(g h),Ea= 37 kJ/mol, specific reaction rate at 220 °C = 113.8 µmol/(gPds), and turnover frequency (TOFNoble metal) at 220 °C = 109.7 × 10−3s−1). The high catalytic performance of the 0.37AuPd2.72/TiO2sample was attributed to the good dispersion of AuPd2.72NPs, the strong redox ability, the large ethyl acetate adsorption capacity, and the strong interaction between AuPdxand TiO2. Acetaldehyde, ethanol, and acetic acid are the main intermediates in the oxidation of ethyl acetate, and the loading of AuPdxNPs effectively reduces the formation of the toxic by-product acetaldehyde. The oxidation of ethyl acetate over the 0.34AuPd2.09/TiO2sample might occur via the pathway of ethyl acetate → ethanol → acetic acid → acetate → CO2and H2O. We believe that the obtained results may provide a useful idea for the design of bimetallic catalysts under industrial conditions and for understanding the VOCs oxidation mechanisms.Keywords:supported Au–Pd nanocatalyst;ethyl acetate oxidation;strong electrostatic adsorption;sulfur dioxide resistance;reaction mechanism
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FUEL
·
2023
·
IF 7.4
Zhongchun Yuan,Tingting Cao,Min Deng,Jun Ma,Shuo Geng,Chunliang Yang,Yuan Ren,Mengqin Yao,Fei Liu,Xiaodan Wang
It is very crucial but still a huge challenge to develop efficient and durable catalysts to promote hydrogen production from formic acid (FA). Herein, three CeO 2 with structurally well-defined different shapes, i.e., sCeO 2 (spheres), rCeO 2 (rod) and oCeO 2 (octahedral), are prepared, and their effect on the crystal faces and oxygen vacancy over the constructed heterostructure catalysts (Pd-CeO 2 /C) have been intensively investigated in the FA dehydrogenation. Pd-sCeO 2 /C outperforms the other catalysts with a turnover frequency (TOF) value of 2691 h −1 and selectivity to hydrogen of 100 % at 30 °C. A synergism between the CeO 2 (1 1 0) facet and more oxygen vacancies is considered to be key to obtaining the high reactivity. Moreover, biomass carbon promotes the dispersion of Pd-CeO 2 heterostructures due to its large specific surface area and causes more defects in the Pd-CeO 2 /C. Combined with in-situ FTIR and density functional theory (DFT), it is speculated that FA is decomposed through formate pathway over the Pd-sCeO 2 /C. This work thus provides a reasonable design and controllable synthesis strategy for the effective application of FA as an available liquid phase hydrogen storage material.
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AICHE JOURNAL
·
2023
·Vol. 69
·期 7
·e18085
·
IF 3.7
Wei Wang,Baian Pu,Chi Ma,Chengxiang Shi,Lun Pan,Xiangwen Zhang,Ji-Jun Zou
Cyclopropane derivates are appealing to synthesis of high-energy-density fuels because of the high strained energy of the three-numbered ring. The catalytic cyclopropanation of olefin with diazomethane is very effective to construct the carbocycle. The majority of the catalysts employed are nonrecyclable homogeneous compounds. Herein, we report cyclopropanation of polycyclic olefins catalyzed by heterogeneous Pd/C. The optimal cyclopropanation conditions were explored utilizing dicyclopentadiene as model substrate and a series of polycyclic olefins were cyclopropanated with high yield. Additionally, the catalyst has good recyclability and stability, as shown by characterizations as well as the fact that no inactivation happens after cyclopropanation. The synthesized cyclopropane derivates exhibit good fuel characteristics like high density (1.006–1.087 g/cm 3 ), high volumetric net heat of combustion (42.58–46.45 kJ/cm 3 ), good low-temperature and combustion performance. This work shows industrial potential for cyclopropanation of polycyclic olefins with diazomethane.
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ChemistrySelect
·
2023
·Vol. 8
·期 13
·e202202681
·
IF 2.1
Qing-Qing Pang,Xi-Zheng Fan
Graphical The ultra-fine Pd nanoparticles (NPs) are constructed by strong electrostatic adsorption strategy to ensure ample active sites, further enhance the light absorption intensity and optimize the separation efficiency of electron and hole, contributing to dramatically promote the performance of photocatalytic CO 2 reduction and stability in the gas-solid phase system. The photocatalytic CO 2 converted into the value-added products is regarded as a green strategy for the conversion and utilization of energy. Herein, we develop a commodious SEA (strong electrostatic adsorption) strategy to synthesize Pd-based photocatalysts with ultra-fine Pd NPs (Pd/TiO 2 −S−B). As verified by experiments and characterizations, the ultra-fine Pd NPs can inexorably heighten the reaction activity of catalyst, because it can provide several functions consist of improving the carrier separation efficiency, light absorption and CO 2 molecules adsorption. Meanwhile, the interaction of Pd and substrate can prevent the agglomeration of Pd NPs in reaction process. The designed Pd/TiO 2 −S−B contributes excellent performance in a gas-solid system. The yields of CO (105.1 μmol/g-cat) and CH 4 (254.3 μmol/g-cat) detected, are about 5.25 and 6.24-fold higher than those of pristine TiO 2 . Pd/TiO 2 −S−B also exhibits the forceful stability with acceptable decline of catalytic activity after three cycles. This opens the door for the preparation of high-performance and steady photocatalysts by reliable and effortless strategies toward CO 2 reduction.
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Catalysts
·
2023
·Vol. 13
·期 4
·651
·
IF 3.9
Jiaqi Du,Yidan Peng,Xu Guo,Guoliang Zhang,Fengbao Zhang,Xiaobin Fan,Wenchao Peng,Yang Li
Researchers studying heterogeneous catalysis are intrigued by single-atom catalysts (SACs) due to their ultrahigh atomic utilization. However, only a few reports on SAC-catalyzed classical organic transformations are available. In this work, atomically dispersed Pd sites are confined to a ZrO2hybridized N-doped carbon skeleton with a smart design. UiO-66-NH2is used to anchor Pd atoms by the coordination of the donor atoms including lone pairs of electrons and metal atoms. Subsequently, the in situ introduction of ZrO2doping is achieved using pyrolysis, which helps improve the catalytic performance by modulating the electronic state. The Pd@ZrO2/N–C catalyst obtained from the unique design exhibits a high yield (99%) in eco-friendly media with an extremely low noble metal dosage (0.03 mol% Pd) for the Suzuki reaction. Moreover, Pd@ZrO2/N–C remains highly active after being reused several times and possesses versatility in a variety of substrates. This strategy offers a feasible alternative to designing SACs with atomically dispersed noble metals for heterogeneous reactions.Keywords:palladium;heterogeneous catalyst;Suzuki reaction;ZrO2doping;N-doped carbon
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ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Wenxia Fan,Ani Wang,Lei Wang,Xin Jiang,Zhenzhen Xue,Jinhua Li,Guoming Wang
Delicate design and bottom-up synthesis of hollow nanostructures for oxygen evolution electrocatalysts is a promising way to accelerate the reaction kinetics of overall water splitting. Herein, an efficient and versatile strategy for the controllable preparation of Pd–Cu alloy nanoparticles encapsulated in carbon nanopillar arrays (PD–Cu@HPCN) is developed. Core–shell structured MOF@imidazolium-based ionic polymers (ImIPs) have been prepared and adopted as a template, along with the decomposition of the inner Cu–MOFs when an anion exchange occurs between sodium tetrachloropalladate in solution and bromides in the external ImIP shell. Pd nanoparticles will be highly dispersed in the resulting Pd–Cu@HO-ImIP array, and subsequent topotactic transformation generates Pd–Cu@HNPC. No hazardous reagents or tedious steps are used to remove the inner Cu–MOF templates in contrast to the traditional top-down methods. Remarkably, the Pd–Cu@HPCN catalyst possesses outstanding oxygen evolution reaction (OER) activity, including small overpotential with 10 mA cm–2 at an overpotential of 188 mV, a large double layer capacitance (73.8 mF cm–2), and high stability (20 h). This simple, green, and efficient synthesis methodology represents a new way to design metal alloys for OER electrocatalysts or other electrocatalytic devices.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2022
·
IF 9.136
Jing Yang,Heng-Quan Chen,Fen Qiao,Xifeng Zhu,Tao Wang,Wei-Ping Pan
Engineering metal-based nanoarchitectures and their atomic-scale arrangement is a promising avenue for enhanced mercury adsorbent activities. Interactions between metal single atoms and substrates result in regulated transitions between distinct reaction processes that boost mercury adsorption activity. Herein, a novel sorbent of porous Co 3 O 4 with Palladium atomic dispersed was successfully prepared by one-step pyrolysis of zeolitic imidazolate framework 67 (ZIF-67) precursors. Via engineering single Pd atoms into ZIF-derived Co 3 O 4 (Pd 1 /Co 3 O 4 -ZIF), the strong metal-support interaction (SMSI) activated the reducibility of Co 3+ in porous Co 3 O 4 to efficiently adsorb and oxidize Hg 0 , enhancing its mercury removal efficiency. Specifically, Pd 1 /Co 3 O 4 -ZIF exhibited superior sorption performance for Hg 0 over a broad range of temperatures (30–350 °C) and high gaseous hourly space velocity (about 555,500 hr −1 ) with the average Hg 0 removal efficiency higher than 98%. The strategy of constructing atomic active sites on the surface of porous metal-oxide to convert adsorbed Hg 0 into HgO is a promising approach to solve the problem that Hg 0 in flue gas is challenging to remove. Density functional theory (DFT) calculation further proved that the existence of a single Pd site on the surface of Co 3 O 4 significantly reduced the energy barrier of Hg 0 to HgO at the atomic level. This work contributed to a thorough comprehension of the structural and adsorption properties of the ZIF-derived Co 3 O 4 sorbent engineering with a single atom and enabled the efficient capture of elemental mercury in flue gas by such ZIF-derived sorbent.
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Journal of Materials Chemistry B
·
2019
·Vol. 7
·期 15
·2499-2511
·
IF 5.047
Qianglan Lu,Sun Qi,Peishan Li,Lifang Yang,Shan Yang,Yidan Wang,Yu Cheng,Yilin Song,Siyu Wang,Fengping Tan,Nan Li
Photothermal therapy (PTT) has shown promising potential and bright prospects in damaging primary tumors; however, it is limited to metastatic and recrudescent tumors as PTT requires straightforward light irradiation. Moreover, metastatic and recrudescent tumor immunosuppression due to host T-cell antitumor activity is dramatically impeded because of programmed cell death 1 ligand (PD-L1) and programmed cell death receptor 1 (PD-1) pathways and immune checkpoint blockade (ICB) therapy. In this work, we demonstrate that PTT combined with ICB could not only eliminate primary tumors, but also prevent tumor metastasis to the lungs/liver. In particular, we have designed immunoadjuvant nanomedicine carriers on the basis of polydopamine (PDA) simultaneously loaded with resiquimod (R848)—a kind of toll-like receptor 7 (TLR7) agonist—and carbon dots (CDs)—a fluorescent agent. This nanomedicine is defined as PDA-PEG-R848-CD nanoparticle (NP). The multitasking PDA-PEG-R848-CD NPs can destroy 4T1 breast tumors by PTT under near-infrared laser irradiation in addition to generating tumor-associated antigens. Moreover, the PTT effect triggered the release of R848, thereby inducing a strong antitumor immune response. Meanwhile, this synergistic therapy also shows the abscopal effects by completely inhibiting the growth of untreated distant tumors by effectively triggering the tumors infiltrated by CD3/CD8. Such findings suggest that PDA-PEG-R848-CD NPs could significantly potentiate the systemic therapeutic efficiency of PD-L1 checkpoint blockade therapy by activating both innate and adaptive immune systems in the body.
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高影响因子
FUEL PROCESSING TECHNOLOGY
·
2019
·
IF 4.507
Tao Xie,Jing-Pei Cao,Chen Zhu,Xiao-Yan Zhao,Ming Zhao,Yun-Peng Zhao,Xian-Yong Wei
Selectively cleaving the C O bonds in lignin to produce aromatic products are challenging problems. Currently, catalytic hydrogenolysis of C O bonds in lignin requires harsh conditions. Herein, selectively cleaving C O bond of benzyl phenyl ether (BPE) was studied over Pd/AC, Ru/AC and Ni/AC. Among these catalysts, Pd/AC efficiently cleaved C O bond in BPE under super mild conditions (25 °C, 2 h and 0.1 MPa H 2 ). The products were toluene and phenol without hydrogenation of the aromatic ring . The main competitive step of hydrogenolysis and hydrogenation is sensitive to reaction temperature over Pd catalyst. A mild temperature is preferred for hydrogenolysis, since the H species nearby the oxygen atom are more strongly adsorbed than nearby the benzene rings . With the different H-donor solvents, the highest conversion of BPE was obtained in isopropanol. Based on the experiments, the reactions occurred via cleavage of the C aliphatic -O bond in BPE and the synergetic effects between the H from absorbed H 2 on the surface of the Pd and the intermediates radicals of benzyl and phenoxy should be the key points to such an optimum result.
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