Journal of Physical Chemistry C
·
2021
·
IF 4.126
Weiyu Wang,Qiang Wang,Yueying Chu,Guodong Qi,Shenhui Li,Jun Xu,Feng Deng
Alkyne semihydrogenation offers a key approach for the synthesis of stereodefined molecules. The stereoselective hydrogenation of propyne to propene over Al2O3-supported Pd–Ag bimetallic catalysts is studied by using parahydrogen-induced polarization (PHIP) NMR technique. The supported catalysts were prepared by an incipient-wetness impregnation method, and their properties were systemically tuned by altering Pd and Ag components. Structural characterization by X-ray diffraction, infrared spectra, and transmission electron microscope shows the formation of highly dispersed bimetallic Pd–Ag nanoparticles with random alloy structures on Al2O3 support. For the hydrogenation of propyne over Pd–Ag catalysts with higher Ag concentration, the adsorbed protons are mostly restricted on the active Pd ensembles, which favors a higher pairwise hydrogen addition to propyne, leading to a stronger PHIP effect. The product stereoselectivity measurements show that the pairwise syn-addition to propyne increases with Ag content in the Pd–Ag alloy. The reaction conditions impact the pairwise hydrogenation stereoselectivity. A lower H2/propyne ratio of reactant flow or a higher total reactant flow rate enhances the apparent pairwise syn-addition stereoselectivity, which can be accounted for by the suppressed cis–trans isomerization process and/or a higher intrinsic pairwise syn-addition selectivity.
研究领域:
催化化学
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物理化学
·
材料科学
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ELECTROCHIMICA ACTA
·
2020
·
IF 6.215
Hui Jiang,Lin Liu,Kai Zhao,Zhen Liu,Xinsheng Zhang,Shuozhen Hu
Nitrogen doping was widely used to increase the electronic density of carbon materials and to enhance the adsorption of the supported metal catalysts . However, the exact interaction between various doped nitrogen species and palladium (Pd) have rarely been reported for formic acid electrooxidation (FAO). In this study, the effect of the doped pyridinic-N and pyrrolic-N on the electronic structure and the electrochemical activity of Pd toward FAO are investigated. The oxidation state of Pd is reduced and more metallic Pd is formed when Pd nanoparticles supported on pyridinic-N and pyrrolic-N doped carbon materials . Density functional theory (DFT) calculations simulate that the adsorption energy of HCOO* and *COOH on Pd/pyrrolic-N are lower than those on Pd/pyridinic-N. Both DFT and electrochemical measurements suggest that the FAO activity of Pd is more correlated with the pyrrolic-N than pyridinic-N. The catalyst contains more pyrrolic-N species exhibits higher electrochemical activity and faster kinetics for FAO reaction. Moreover, Pd 2+ -N complexes are formed in all the nitrogen doped catalysts and display good activity for FAO. In this study, Pd supported on urea treated carbon (Pd/UR) owns the highest content of pyrrolic-N and exhibits the best activity for FAO.
研究领域:
材料科学
·
电化学
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ACS Applied Materials & Interfaces
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2020
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IF 8.758
Aleksei Chalgin,Wenlong Chen,Qian Xiang,Yi Wu,Fan Li,Fenglei Shi,Chengyi Song,Peng Tao,Wen Shang,Jianbo Wu
The urgent need of catalysts with improved performances toward the hydrogen evolution reaction (HER) is still one of the crucial issues for the water splitting electrocatalysis. Herein, we exhibit that the HER activity of the Pd nanocubes could be improved by selecting the appropriately shaped titania nanocrystals as support. In particular, we used Pd nanoparticles with (100)-facet exposed to show that the HER performance of Pd cubes can be improved in both acidic and alkaline electrolyte media when combined on the anatase TiO2 nanocrystals. Furthermore, we have also investigated the facet effect of TiO2 on the performance in detail, which indicated stronger catalytic activity when (001)-TiO2 was used rather than (mix 101/001)-TiO2 and (101)-TiO2. The electron-transfer-induced improvement of HER activity of Pd/TiO2 was assessed by electron energy loss spectroscopy (EELS). Thereafter, the combined support materials with suitable facet exposed can give an additional adjusting path to regulate the HER activities of Pd nanocatalysts, which henceforth can further contribute to a novel way for tuning other catalysts with good electrocatalytic properties.
研究领域:
材料科学
·
电化学
·
纳米技术
·
催化
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ACS Sustainable Chemistry & Engineering
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2026
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IF 7.3
Jun Zhou,Liwen Ma,Yue Yin,Zhaodong Li,Sitong Liu,Junchao Ma,Yunong Li,Xiaoqing Cao,Song Li,Gaowu Qin
The green and selective oxidation of silanes to silanols has attracted considerable attention owing to its extensive applications across various industries. In this study, we introduce a novel instantaneous low-voltage microplasma electrolytic oxidation (ILVPEO) strategy to fabricate a highly efficient Pd/MgO/Mg catalytic system for the selective oxidation of silane to silanol. This approach leverages in situ microplasma effect to simultaneously decompose [PdCl4]2– and oxidize the Mg substrate, yielding Pd/MgO/Mg composites that features ultrasmall Pd nanoparticles (2.1 nm with high monodispersity) uniformly anchored on a porous and hydrophilic MgO support. These characteristics endow the catalyst with outstanding performance in the oxidation of phenylmethyldimethylsilane (PhMe2SiH) to the corresponding phenylmethyldimethylsilanol (PhMe2SiOH), achieving a remarkable turnover frequency (TOF) of 11,698 mol mol–1 h–1(129,260 mol mol–1 h–1), significantly surpassing conventional systems. Notably, the reaction proceeds using water as the primary oxygen source and generates hydrogen as the only byproduct, aligning closely with the principles of green chemistry. Moreover, the Pd/MgO catalyst demonstrates excellent durability, maintaining over a 90% product yield across 20 consecutive reaction cycles. It also displays broad substrate compatibility, efficiently oxidizing a diverse array of silanes with steric effects influencing the activity. This work presents a sustainable and scalable catalytic platform for silane oxidation, offering substantial potential for green industrial applications.
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ACS Applied Nano Materials
·
2026
·
IF 5.8
Xinru Wang,Lei Jin,Wenqian Li,Yu-Shi He,Jinglin Mu,Weimin Zhang
Electrocatalytic hydrogenation dechlorination (EHDC) has emerged as a promising and environmentally benign strategy for the degradation of chlorinated phenols (CPs), owing to its green process characteristics and the absence of hazardous byproducts. Achieving high EHDC efficiency necessitates both a highly active electrocatalyst and optimized reaction conditions. In this work, we fabricated a Pd/Co3O4 electrode, comprising ultralow-loading Pd nanoparticles (0.011 mg Pd cm–2) supported on a Co3O4 nanoarray grown on carbon fiber paper (CFP), for EHDC applications. The well-defined array structure facilitates uniform potential and current density distribution while also expanding the number of electroactive sites. Electrochemical and theoretical analyses reveal that abundant oxygen vacancies (OVs) in Co3O4 induce a spatial charge redistribution in the Pd/Co3O4 heterostructure, thereby strengthening the metal-support interaction (SMSI). This optimization of geometric and electronic properties significantly enhances both hydrogen evolution capability and EHDC performance. Under optimized operational parameters, including pH, substrate concentration, and applied potential, the Pd/Co3O4/CFP electrode achieves nearly complete degradation (close to 100%) of 10 mg·L–1 4-chlorophenol (4-CP) within 180 min at a cathodic potential of −0.8 V vs Ag/AgCl, with phenol (P) as the main product. The mass activity (MA) for 4-CP dechlorination reaches 1.0289 min–1 mg–1. Density functional theory (DFT) calculations further illustrate that the underlying oxygen vacancy rich Co3O4 modulates the electronic structure of Pd, boosting hydrogenation capacity and EHDC efficiency. These findings underscore the great potential of the Pd/Co3O4/CFP electrode as an efficient and practical electrocatalyst for EHDC processes.
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Materials Today Bio
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2026
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IF 11
Xueping Luo,Yixin Liu,Guangmiao Chen,Xinrui Ma,Pingping Xu,Yutong Li,Longyu Zheng,Rongrong Zheng,Youqin Xu,Shiying Li,Linping Zhao
Ferroptosis, a form of regulated cell death that is iron-dependent and driven by the accumulation of lipid peroxides (LPO), has emerged as a promising avenue for enhancing tumor immunogenicity and augmenting immune checkpoint blockade (ICB) efficacy. In this study, we demonstrated that dBET57, a BRD4-targeting PROTAC, potently suppresses the expression of GPX4, the master negative regulator of ferroptosis, thereby triggering ferroptotic cell death, while concurrently downregulating PD-L1 to reverse immune evasion. Based on this, we developed a self-assembled nano-PROTAC platform, termed dBET@TF, designed to amplify ferroptosis and potentiate colorectal cancer immunotherapy. Specifically, dBET@TF was constructed via self-assembly of dBET57, tannic acid, and Fe 3+ , which endowed the formulation with acid-responsive drug release capability and significantly improved its intracellular delivery efficiency. Mechanistically, dBET@TF promoted ferroptosis through iron accumulation and GPX4 depletion, triggering robust immunogenic cell death (ICD). Concurrently, BRD4 degradation mediated by dBET@TF durably suppressed PD-L1 expression, reprogramming the tumor microenvironment to foster enhanced immune activation, characterized by increased infiltration of natural killer (NK) cells and cytotoxic T lymphocytes (CTLs). As a result, dBET@TF significantly potentiated the therapeutic response to αPD-1 in both primary tumor and experimental lung metastasis models. Overall, this work establishes a novel PROTAC-based therapeutic strategy that leverages BRD4 degradation to amplify ferroptosis and remodel antitumor immunity, offering a promising approach to potentiate colorectal cancer immunotherapy.
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PubMed
高影响因子
ADVANCED MATERIALS
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2026
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IF 29.1
Chao Peng,Xiong Wang,Lang Chen,Shuang-Feng Yin
Selective photocatalytic upgrading of glycerol to glycolaldehyde is intrinsically challenging because, under a conventional C–C cleavage scenario, the carbon-based selectivity of a C2 product is, in principle, capped at 66.67%. Here, a size-regulated Pd on TiO 2 platform as an efficient photocatalyst realized selective oxidation of glycerol into glycolaldehyde with selectivity up to 87.54%. As the Pd size increases from single atoms to nanoparticles, both glycerol conversion and glycolaldehyde selectivity increase monotonically, reaching 36.52% conversion and a glycolaldehyde formation rate of 12.05 mmol g ‒1 h ‒1 . Combined in situ spectroscopy, isotope-labeling experiments, and density functional theory calculations reveal that increasing Pd size switches glycerol adsorption from a symmetric terminal–terminal mode to an asymmetric terminal–secondary mode, thereby promoting C–C activation and enabling a radical-mediated cleavage-recoupling route toward glycolaldehyde. Isotopic liquid chromatography-mass spectrometry verifies C–C recombination after bond cleavage, which accounts for the glycolaldehyde selectivity exceeding the conventional 66.67% carbon limit, water as a direct contributor to •OH generation, and oxygen incorporation into the products. This work establishes a mechanistic framework in which metal size alters the interfacial adsorption geometry and reaction energy, thereby providing a general strategy for the selective photocatalytic valorization of polyol biomass molecules.
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ACS Sensors
·
2026
·Vol. 11
·期 8
·7558-7571
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IF 10.9
Cao Chen-Yang,Cheng Chen,Yue Li-Juan,Xie Ke-Feng,Dong Hua-Dong,Yang Xuan-Yu,Zhang Yong-Hui
Rational design of interfacial electronic structures and defect sites is pivotal for advancing chemiresistive gas sensing, yet achieving synergistic modulation remains a formidable challenge. Herein, we report a ternary Pd–HPW–ZnO heterostructure constructed via the integration of phosphotungstic acid (HPW) clusters and Pd nanoparticles onto porous ZnO nanosheets. This unique architecture establishes a robust electronic coupling network, where HPW acts as an electron sink, inducing electron depletion in both ZnO and Pd species to form electron-deficient Pd sites. This electronic modulation, corroborated by XPS and DFT calculations, significantly optimizes the Pd d-band center and enhances the surface Lewis acidity. Furthermore, the synergistic interaction triggers a substantial enrichment of oxygen vacancies and facilitates the spillover of active oxygen species. Consequently, the optimized sensor exhibits an extraordinary response of 2016.70 to 50 ppm triethylamine (TEA) at a low operating temperature of 110 ° C, surpassing pristine ZnO by nearly 60-fold. The sensor also demonstrates ultrafast response/recovery kinetics (16/150 s), excellent selectivity against interfering volatiles, and robust long-term stability. This work provides a paradigm for boosting sensing performance through precise interfacial electronic regulation and defect engineering in multicomponent heterostructures.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2026
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IF 6.7
Yongjing Guo,Hangshuo Feng,Fan Zhao,Li Yang,Qiuni Zhao,Dongyang Li,Shunping Zhang,Yi Xia,Ming Hou,Shenghui Guo
Controlling the morphology to modify the properties of materials is an effective strategy to enhance the response performance of gas sensing materials. Herein, a three-dimensional (3D) nanoflower-like tin disulfide (SnS 2 ) structure assembled from nanosheets was synthesized. Subsequent annealing treatment partially oxidizes the nanosheets, inducing random stacking of the nanosheets, thereby increasing the structural disorder analogous to opened hair cuticle. This structure was further decorated by zero-dimension (0D) palladium nanoparticles (Pd NPs) to construct 0D-3D hierarchical structure for hydrogen (H 2 ) detecting. The H 2 sensing experiment results showed that optimized Pd/SnO 2 /SnS 2 gas sensor exhibits a high response of 1260% to 1000 H 2 at 275 °C, along with fast response/recovery time of 18/67 s. The gas sensor exhibited a low limit of detection (1.74 ppm). The above sensing performance is attributed to the unique hierarchical assembled nanoflower-like architecture, which was transformed from an initial closed hair-cuticle-like morphology into an open one by annealing. This newly formed open structure, coupled with the composite formation with Pd NPs, collectively facilitates both the carrier charge transfer process and the adsorption/desorption reaction of H 2 . This work demonstrates a promising strategy for developing high-performance H 2 sensors through morphology-engineered and noble metal-functionalized transition metal dichalcogenides.
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INTERNATIONAL IMMUNOPHARMACOLOGY
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2026
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IF 5.6
Jing Gong,Chengjiang Fan,Jianing Chen,Shuhui Xu,Haizhong Jiang,Desen Sun,Qiang Chen,Qi Liao,Yang Xi
Colorectal cancer (CRC) remains one of the most prevalent and malignant cancers worldwide. Although various therapeutic strategies have been developed, CRC patients often exhibit poor responses. The combination of chemotherapy with immune checkpoint inhibitors represents a promising new treatment approach. However, pervasive drug resistance and significant interindividual variability in treatment efficacy remain major challenges, highlighting the urgent need to elucidate the underlying molecular mechanisms for improved therapy. In this study, we demonstrated that gemcitabine (GEM) exerts therapeutic effects against CRC. Notably, when combined with an anti-PD-L1 immune checkpoint inhibitor, GEM synergistically enhanced antitumor immunity, as evidenced by an increased infiltration of CD8 + T cells. Additionally, the population of anti-tumor IFN-γ and TNF-α-producing CD8 + T cells was elevated. We also observed significantly upregulated PD-L1 expression in both human and mouse CRC cell lines (HCT116, MC38, and CT26) following GEM treatment, which was further confirmed at the cell surface level. Mechanistically, GEM was found to stimulate lactate metabolism and promote lactylation of the PD-L1 protein, which could be reversed by inhibiting lactate dehydrogenase or pyruvate kinase. Furthermore, GEM delayed the degradation of PD-L1 protein confirmed by cycloheximide treatment. In addition, we also identified increased lactylation of H3 upon GEM treatment, suggesting transcriptional activation of PD-L1. Together, our findings provide novel insights into the mechanism of GEM in CRC treatment and support the future development of combined chemo-immunotherapeutic strategies.
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TURKISH JOURNAL OF CHEMISTRY
·
2026
·Vol. 50
·期 3
·285-299
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IF 2
LI JUANHONG,WANG SUQIN,LIU XIN,LIU FENG
A [H]-accelerated catalytic Fenton system was developed using Pd/UiO-66(Zr)-F4 as the catalyst. This system enabled the regeneration of Fe²⁺ and facilitated the continuous generation of both ·OH and 1O2 through [H]-mediated electron transfer at ambient temperature and pressure. Under the conditions of 0.2 g L−1 catalyst (Pd loading 0.516 wt%), 25 μM Fe2+, 60 mL min−1 H2 flow (as the [H] source), 20 mM H2O2, and pH 3, approximately 89% of carbamazepine (initial concentration 20 mg L−1) was degraded within 3 h using trace iron. However, the catalytic activity of Pd/UiO-66(Zr)-F4 gradually declined from 89% to 53% over six reaction cycles. This decrease was likely due to loss of specific surface area caused by microstructural degradation associated with hydrogen spillover effects.
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SmartMat
·
2026
·Vol. 7
·期 2
·e70073
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IF 14.3
Mengjie Xu,Min Hao,Jing Yu,Junfeng Du,Shuai Zhang,Haibin Chu,Yaping Du
The electrocatalytic nitrate reduction reaction (NO 3 RR) provides a sustainable route for nitrogen pollution remediation and ammonia production under ambient conditions. However, the process involves sluggish multi-electron/proton transfer and suffers from competing hydrogen evolution (HER) which severely limits efficiency and selectivity. Herein, we construct a Pd x -CeO 2 /C composite catalyst, in which strong interactions between Pd and CeO 2 induce interfacial electronic redistribution, thereby effectively modulating the Pd electronic structure. This interfacial coupling enhances water dissociation, accelerates the generation of reactive *H, and promotes its spillover from Pd to CeO 2 . In-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) confirms that hydrogen spillovers facilitate stepwise hydrogenation of intermediates while suppressing HER. Density functional theory calculations further reveal that Pd-Ce interactions inhibit HER and enable N─O side-on adsorption, shifting the potential-determining step and lowering the reaction barrier, thus boosting electrocatalytic activity. As a result, the optimized 5 wt.% Pd-CeO 2 /C delivers a Faradaic efficiency of 98.0% for ammonia at −0.4 V (vs. RHE), and achieves an ammonia yield rate of 4.17 mmol/(mg Pd ∙h) at −0.6 V. This work offers new insights into the application of interfacial engineering for efficient electrocatalytic ammonia synthesis.
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