CATALYSIS COMMUNICATIONS
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2016
·
IF 3.389
Mazloom Shah,Qing-Xiang Guo,Yao Fu
The Pd, Ni, Ni-Sn, Cu and Ag@Pd nanocatalyst having different shape and size were used for direct dehydrogenation of cyclic ketones to the corresponding phenols in the presence of O 2 as the oxidant. Among all catalyst tested, metallic Pd-1 nanoparticles exhibited excellent catalytic performance both in presence and absence of p-toluenesulfonic acid. The dehydrogenation of cyclohexanone catalyzed by Pd-1 nanocatalyst led to a 93% yield of the desired cyclohexenone and phenol. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed that there was no change in morphology, crystal phases and particles size of Pd-1 nanocatalyst after the reaction.
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Nature Communications
·
2024
·Vol. 15
·期 1
·1-10
·
IF 14.7
Shi Fenglei,Tieu Peter,Hu Hao,Peng Jiaheng,Zhang Wencong,Li Fan,Tao Peng,Song Chengyi,Shang Wen,Deng Tao,Gao Wenpei,Pan Xiaoqing,Wu Jianbo
Corrosion of electrocatalysts during electrochemical operations, such as low potential - high potential cyclic swapping, can cause significant performance degradation. However, the electrochemical corrosion dynamics, including structural changes, especially site and composition specific ones, and their correlation with electrochemical processes are hidden due to the insufficient spatial-temporal resolution characterization methods. Using electrochemical liquid cell transmission electron microscopy, we visualize the electrochemical corrosion of Pd@Pt core-shell octahedral nanoparticles towards a Pt nanoframe. The potential-dependent surface reconstruction during multiple continuous in-situ cyclic voltammetry with clear redox peaks is captured, revealing an etching and deposition process of Pd that results in internal Pd atoms being relocated to external surface, followed by subsequent preferential corrosion of Pt (111) terraces rather than the edges or corners, simultaneously capturing the structure evolution also allows to attribute the site-specific Pt and Pd atomic dynamics to individual oxidation and reduction events. This work provides profound insights into the surface reconstruction of nanoparticles during complex electrochemical processes.
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Nature Communications
·
2024
·Vol. 15
·期 1
·1-10
·
IF 14.7
Fang Cao,Xu Chang,Zhang Wei,Zhou Meng,Tan Dong,Qian Lixia,Hu Daqiao,Jin Shan,Zhu Manzhou
Dual emission (DE) in nanoclusters (NCs) is considerably significant in the research and application of ratiometric sensing, bioimaging, and novel optoelectronic devices. Exploring the DE mechanism in open-shell NCs with doublet or quartet emissions remains challenging because synthesizing open-shell NCs is difficult due to their inherent instability. Here, we synthesize two dual-emissive M 1 Ag 13 (PFBT) 6 (TPP) 7 (M = Pt, Pd; PFBT = pentafluorobenzenethiol; TPP = triphenylphosphine) NCs with a 7-electron open-shell configuration to reveal the DE mechanism. Both NCs comprise a crown-like M 1 Ag 11 kernel with Pt or Pd in the center surrounded by five PPh 3 ligands and two Ag(SR) 3 (PPh 3 ) motifs. The combined experimental and theoretical studies revealed the origin of DE in Pt 1 Ag 13 and Pd 1 Ag 13 . Specifically, the high-energy visible emission and the low-energy near-infrared emission arise from two distinct quartet excited states: the core-shell charge transfer and core-based states, respectively. Moreover, PFBT ligands are found to play an important role in the existence of DE, as its low-lying π * levels result in energetically accessible core-shell transitions. This novel report on the dual-quartet phosphorescent emission in NCs with an open-shell electronic configuration advances insights into the origin of dual-emissive NCs and promotes their potential application in magnetoluminescence and novel optoelectronic devices.
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NEW JOURNAL OF CHEMISTRY
·
2024
·Vol. 48
·期 26
·11794-11801
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IF 2.7
Mingming Du,Anxian Peng,Hongyue Liu,Qiyun Li,Likai Dai,Zheng Fang,Ganning Zeng,Huimei Chen,Rongjun Yan
The photocatalytic conversion of endless solar energy into storable and usable chemical energy, such as photocatalytic hydrogen peroxide production, is promising and attractive. However, a satisfactory hydrogen peroxide yield has not been achieved using photocatalysts due to the rapid recombination of photoexcited carriers and the rapid decomposition of H2O2. Herein, a polymer polyethyleneimine (PEI)-assisted Pd metal loading BiOCl nanosheet photocatalyst (Pd/PEI/BOC) is designed to achieve higher photocatalytic activity. Experimental results show that compared to the Pd/BOC catalyst with a Pd loading of only 0.26 wt%, the Pd/PEI/BOC catalyst can achieve a higher Pd loading of 0.45 wt%, which is due to the obvious shifting of the isoelectric point (IEP) of BiOCl from the pH value of 4.1 to 8.4 in the presence of PEI, leading to enhanced immobilization. Furthermore, H2O2 decomposed more slowly for the Pd/BOC catalyst modified by PEI. In addition, Pd can significantly enhance the separation of electrons–holes and light absorption range, especially for visible light. Therefore, under simulated sunlight, this Pd/PEI/BOC catalyst displayed a higher H2O2 production ability of 3700.23 μmol g−1 h−1.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Xi-Guang Wang,Lu-Yang Qiao,Li-Yuan Xu,Yun-Yun Zeng,Zhi-Shen Huang,Shan-Shan Zong,Jin-Xiang Wang,Zhang-Feng Zhou,Yuan-Gen Yao
The intrinsic nature of irreducible oxides (e.g. Al 2 O 3 ) makes it hard to tune the charge state of supported late-transition metals, then difficult to adjust the selectivity of catalysts in CO 2 hydrogenation. Herein, we find that modifying the Pd/Al 2 O 3 catalyst with alkali metals (especially potassium) is efficient to boost the CO formation in CO 2 hydrogenation. In comparison to Pd/Al 2 O 3 , approximately twenty-fold promotion in reverse water–gas shift (RWGS) rate was achieved on K-modified catalysts with proper K/Pd proportions. Combined structural characterizations demonstrate that the enhanced Pd-O interactions through K mediation stabilize the ca. 2 nm sized Pd particles as well as the electron-deficient state of Pd, which are robust enough during long-termed evaluation with undamped performance. In situ spectroscopy unveils a bi-dentate *HCOO associated reaction mechanism taking effect on alkali-modified catalysts, which contributes to ∼ 100 % of CO selectivity and 3318.1 mmol∙g Pd -1 ∙h −1 of CO formation rate at 340°C.
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CHEMISTRY OF MATERIALS
·
2024
·
IF 7.2
Shikai Liu,Chuqiao Shi,Chaokai Xu,Haichuan Zhang,Wenqi Li,Valentín Briega-Martos,Qian He,Yimo Han,Yao Yang
CO2 reduction reaction (CO2RR) facilitates the sustainable synthesis of fuels and chemicals. Although copper (Cu) enables CO2-to-multicarbon product (C2+) conversion, Cu-based electrocatalysts, particularly nanocatalysts, face challenges in poor selectivity and stability owing to the highly dynamic nature of Cu atoms under reaction conditions. Core–shell structures present a promising approach to address these issues by modulating the Cu overlayer–substrate interactions with atomic-level precision. Here, we report on Pd@Cu core–shell structures with atomically thin and nanometer-thick Cu overlayers on single-crystal Pd nanocubes with {100} facets promoting the CO2-to-C2+ conversion. The microstructures and surface compositions at the atomically sharp Pd/Cu interface were investigated by atomic-scale scanning transmission electron microscopy (STEM) imaging and electron energy-loss spectroscopy (EELS). Our results reveal that atomic-layer Cu epitaxially grows on Pd and adapts to the lattice of the Pd substrate. The reaction-driven migration of atomic-layer Cu is effectively suppressed on Pd due to the strong Cu–Pd interaction. While Pd only reduces CO2 to C1 products, atomic-layer Cu on Pd can initiate the C2+ production during the CO2RR. Thick Cu overlayers (∼15 nm) on Pd further enhance the C2+ faradaic efficiency while undergoing significant structural reconstruction, with only the 2–3 nm Cu layers near the Pd surface remaining stable and resistant to Cu migration after the CO2RR. We anticipate that Pd@Cu core–shell structures with intermediate Cu shell thickness hold significant potential for enhancing C2+ selectivity while maintaining high stability of nanocatalysts for CO2 reduction to liquid fuels.
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Green Chemical Engineering
·
2025
·
IF 7.6
Ruan Tao,Zhao Lisha,Ouyang Xinping,Li Lifeng,Zhang Wenwei,Qiu Xueqing
The depolymerization of lignin into aromatic monomers with high yield is the bottleneck of high valued utilization of lignin. In this work, a highly dispersed Pd supported on WO 2.72 (Pd/WO 2.72 ) catalyst was prepared for efficient hydrogenolysis lignin. The highly dispersed Pd, high specific surface area, high content of acidic sites, and hydrogen spillover of Pd/WO 2.72 improved the depolymerization efficiency of lignin. In addition, the depolymerized products were alkylated with the reaction solvent to prevent monomers from re-polymerizing, thus further enhancing aromatic monomers yield. Under 320 º C, 6 h, Bio-oil and aromatic monomers yield reached 77.67% and 28.80%, respectively. Among the aromatic monomers, the tert -butyl group substituted products accounted for 65.71%, of which 77.1% were methoxy-free phenols. It was found that the bio-oil had a calorific value of 38.13 MJ/kg and an IC 50 value of 43 mg/L, showing their potential applications as fuels or antioxidant additives.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Daobin Tang,Xuebin Lin,Qi Zhang,Zhenni Wang,Yuhang Liu,Yanqiao Jin,Xinru Wu,Cejun Hu,Pei Yuan
Lignin is continuously investigated by various techniques for valorization due to its high content of oxygen-containing functional groups. Catalytic systems employing hydrolysis‑hydrogenolysis, leveraging the synergistic effect of redox metal sites and acid sites, exhibit efficient degradation of lignin. The predominance of either hydrolysis or hydrogenolysis reactions hinges upon the relative activity of acid and metal sites, as well as the intensity of the reductive atmosphere. In this study, the Pd-MoO x /TiO 2 catalyst was found to primarily catalyze hydrolysis in the lignin depolymerization process, attributed to the abundance of moderate acidic sites on Pd and the redox-assisted catalysis of MoO x under inert conditions. After subjecting the reaction to 240 °C for 30 h, a yield of 48.22 wt% of total phenolic monomers , with 5.90 wt% consisting of diphenols, was achieved. Investigation into the conversion of 4-propylguaiacol (4-PG), a major depolymerized monomer of corncob lignin, revealed the production of ketone intermediates, a phenomenon closely linked to the unique properties of MoO x . Dehydrogenation of the propyl is a key step in initiating the reaction, and 4-PG could be almost completely transformed, accompanied by an over 97 % of 4-propylcatechol selectivity. This distinctive system lays a new theoretical groundwork for the eco-friendly valorization of lignin.
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Cell Metabolism
·
2025
·
IF 30.9
Yizeng Fan,Weichao Dan,Yuzhao Wang,Zhiqiang Ma,Yanlin Jian,Tianjie Liu,Mengxing Li,Zixi Wang,Yi Wei,Bo Liu,Peng Ding,Yuzeshi Lei,Chendong Guo,Jin Zeng,Xiaolong Yan,Wenyi Wei,Lei Li
Itaconate is a metabolite catalyzed by cis- aconitate decarboxylase (ACOD1), which is mainly produced by activated macrophages and secreted into the extracellular environment to exert complex bioactivity. In the tumor microenvironment, itaconate is concentrated and induces an immunosuppressive response. However, whether itaconate can be taken up by tumor cells and its mechanism of action remain largely unclear. Here, we identified solute carrier family 13 member 3 (SLC13A3) as a key protein transporting extracellular itaconate into cells, where it elevates programmed cell death ligand 1 (PD-L1) protein levels and decreases the expression of immunostimulatory molecules, thereby promoting tumor immune evasion. Mechanistically, itaconate alkylates the cysteine 272 residue on PD-L1, antagonizing PD-L1 ubiquitination and degradation. Consequently, SLC13A3 inhibition enhances the efficacy of anti-CTLA-4 (cytotoxic T lymphocyte-associated antigen-4) immunotherapy and improves the overall survival rate in syngeneic mouse tumor models. Collectively, our findings identified SLC13A3 as a key transporter of itaconate and revealed its immunomodulatory role, providing combinatorial strategies to overcome immunotherapy resistance in tumors.
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Materials
·
2025
·Vol. 18
·期 6
·1279
·
IF 3.2
Zisheng Tang,Dafu Zhao,Xiaoqian Wang,Yanhui Jiao,Manrui Liu,Chengqi Liu,Qi Zhang,Shujing Ren,Yong Liu
Enhancing the limited utilization and overall yield of Pt-based catalysts is essential for advancing proton exchange membrane fuel cell technology. Herein, we report a facile one-pot method that utilizes TEG as both a solvent and a reductant to efficiently synthesize a Pd@Pt core-shell icosahedron. By controlling the surface energy between Pd and Pt precursors, we achieved the formation of Pd@Pt core-shell icosahedra, resulting in a fourfold reduction in reaction time and an eightfold increase in yield. Moreover, the core-shell structures exhibited a significant enhancement in electrocatalytic activity, stability, and Pt utilization efficiency. In comparison to commercial Pt/C, the Pd@Pt core-shell icosahedron exhibited efficient mass activity (MA, 1.54 A mg−1Pt) and specific activity (SA, 2.24 mA cm−2Pt) at 0.9 V (vs. RHE), while demonstrating excellent stability with minimal loss of activity even after 10,000 potential cycles. The Pd@Pt icosahedra configuration integrates the advantages of multiply twinned nanostructures, leading to rich electrochemical active surface sites and fast charge transport, thereby improving its catalytic performance and long-term stability during electrocatalytic reactions.
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Nanomaterials
·
2024
·Vol. 14
·期 14
·1188
·
IF 4.4
Hongyang Wu,Chen Chen
The efficient detection of n-butanol, which is in demand for highly sensitive materials, is essential for multiple applications. A nonaqueous method was applied to prepare NiFe2O4nanoparticles (NPs) using benzyl alcohol as a solvent, which shows a size of 7.9 ± 1.6 nm and a large surface area of 82.23 m2/g. To further improve the sensing performance for n-butanol, Pd/PdO functionalization was sensitized with NiFe2O4NPs. Gas sensing results demonstrate that the Pd/PdO-NiFe2O4exhibits an enhanced response of 36.9 to 300 ppm n-butanol and a fast response and recovery time (18.2/17.6 s) at 260 °C. Furthermore, the Pd/PdO-NiFe2O4-based sensor possesses a good linear relationship between responses and the n-butanol concentration from 1 to 1000 ppm, and great selectivity against other volatile organic compounds (VOCs). The excellent sensing enhancement is attributed to the catalytic effects of Pd/PdO, the increase of oxygen vacancies, and the formation of heterojunction between PdO and NiFe2O4. Thus, this study offers an effective route for the synthesis of Pd/PdO-functionalized NiFe2O4NPs to achieve n-butanol detection with excellent sensing performance.
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ACS Catalysis
·
2017
·
IF 10.614
Chengtao Wang,Zhiqiang Liu,Liang Wang,Xue Dong,Jian Zhang,Guoxiong Wang,Shichao Han,Xiangju Meng,Anmin Zheng,Feng-Shou Xiao
The metal-catalyzed selective hydrogenation of biomass-derived molecules is in great demand but is challenging due to the complex reaction pathways. Herein, we report a persuasive example for achieving selective hydrogenation of furfural over Pd catalysts by controllable sorption of molecules in zeolite micropores. The key to this success is fixation of Pd nanoparticles inside of silicalite-1 zeolite with controllable wettability (Pd@S-1-OH) by functionalizing silanol groups into the zeolite framework. In the hydrogenation of furfural as a model reaction, the Pd@S-1-OH catalyst with appropriate hydrophilicity exhibits extraordinary selectivity for the formation of furan, giving furan selectivity as high as >99.9% with a complete conversion of furfural, outperforming the conventional Pd nanoparticles supported on zeolite crystals (Pd/S-1) and S-1 zeolite fixed Pd catalysts without an artificially functionalized silanol group (Pd@S-1). The extraordinary performance of Pd@S-1-OH is reasonably attributed to the controllable diffusion of molecules within the hydrophilic zeolite micropores, which favors the adsorption of furfural and a series of byproducts but promotes the desorption of furan. Very importantly, Pd@S-1-OH is stable and gives the furan productivity of ∼583.3 g gPd–1 day–1 in a continuous test.
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