查找使用阿拉丁产品的科研文献

d-Band Engineering of Layered (Fe1−xNix)3GaTe2 for Enhanced Alkaline Hydrogen Evolution by Ni-Substitutional Doping

Xiaomin Tian,Yuan Cao,Huilin Zhou,Fanjie Tan,Ziqin Zhang,Liying Pei,Yi Ma,Jianzhi Gao,Wenliang Zhu,Minghu Pan

Tuning the d -band electronic structure of non-noble-metal catalysts is a central strategy for an alkaline hydrogen evolution reaction (HER), yet how composition controls the d orbital in multi-Wyckoff-site layered systems remains insufficiently understood. Here, layered (Fe 1- x Ni x ) 3 GaTe 2 single crystals ( x = 0.2–1.0) were synthesized by the self-flux method as a platform to address this question. Single-crystal XRD and EDS confirm that Ni is uniformly incorporated into the parent P6 3 /mmc framework while inducing a composition-dependent lattice evolution. Electrochemical measurements in 1.0 M KOH reveal a clear volcano-shaped composition dependence, peaking at x = 0.6, where the lowest overpotential, the smallest Tafel slope (94 mV dec −1 ), the lowest charge-transfer resistance and the largest double-layer capacitance are simultaneously reached. First-principles calculations show that Ni doping reshapes the Fe-site d orbital strongly composition-dependent rate: the Fe d -band center upshifts rapidly by ~0.5 eV between x = 0.4 and x = 0.6, while the Ni d -band center stays nearly fixed in the same composition range. The maximum of HER activity therefore aligns with a steep upshift of the Fe d -band center rather than with the Ni content itself. Charge-density mapping of (Fe 0.4 Ni 0.6 ) 3 GaTe 2 further demonstrates that the electron-enriched regions are located on the Fe and interlayer Ni3 sublattices that dominate the d states near E F .

Engineering Brønsted Acidity in Metal-Organic Gels via d⁰-Electron Configuration for Wide-Temperature Anhydrous Proton Conduction

Cuiwen Lu,Wenli Wu,Lingfei Li,Feng Zhang,Jiyu Tang,Siyu Sun,Xiaoqin Zou

The development of solid-state proton conductors that operate efficiently across a wide temperature range, from sub-zero to elevated temperatures, remains a significant challenge, hindered by the inherent limitations of water-dependent materials. Herein, we introduce heterometallic sulfates into a bimetallic metal-organic gel (M/Zr-FA-xerogel) via a one-pot synthesis, resulting in the formation of a hierarchical proton conduction network. This innovative strategy concurrently addresses the quantity, quality, and connectivity of proton carriers. In this network, structural defects enhance carrier concentration, while sulfate groups establish extensive hydrogen-bonding pathways. Importantly, we demonstrate that the intrinsic Brønsted acidity of defect sites can be rationally tuned by manipulating the electronic structure of the dopant.Specifically, the d 0 electronic configuration of Ti 4+ serves as an effective electron sink, significantly reducing the proton dissociation barrier, which is critical for cryogenic transport. This integrated design culminates in an adaptive conduction mechanism that transitions from being dominated by acid strength at low temperatures to being limited by carrier concentration at high temperatures. As a result, the optimized Ti/Zr-FA-xerogel exhibits an exceptional anhydrous conductivity of 1.9 × 10 -3 S cm -1 at 233 K, surpassing its counterpart by 3 orders of magnitude, and 5.0 × 10 -2 S cm -1 at 433 K. This research not only develops a novel design strategy for proton conductors operable across a wide temperature range, but also elucidates the intricate interplay between electronic structure, defect chemistry, and proton dynamics in amorphous coordination polymers.

Electronegativity-driven d-band center shifts in Ru–Ni alloys for low methane hydrogenolysis of polyolefin plastics

Qianfeng Zhou,Huijie Li,Shengdong Zhang,Changhu Leng,Chuanya Li,Yongchao Wang,Chenyang Ma,Wanglei Wang,Xiaogang Fu,Lei Zhu,Tengshijie Gao,Cheng Wang,Li-Zhu Wu,Zhi-Jun Li

Ruthenium (Ru) catalysts are highly efficient in the hydrogenolysis of polyolefin waste, converting the waste into valuable alkanes. However, excessive C–C bond cleavage of strongly adsorbed olefin intermediates often leads to low-value byproducts, primarily methane (CH4). In this study, we developed a Ru–Ni bimetallic catalyst supported on silica (RuxNiy/SiO2) that directly modulates olefin intermediate adsorption to suppress CH4 formation during polyolefin hydrogenolysis. By alloying low-electronegativity Ni with high-electronegativity Ru, we shift the Ru d-band center through electron transfer from Ni, weakening the adsorption of olefin intermediates. This modification facilitates hydrogenation and desorption pathways while suppressing excessive C–C bond cleavage. The resulting catalyst achieved complete polyethylene (PE) conversion at 250 °C, with 96.9 wt% liquid product yield and only 2 wt% CH4 production. Gasoline- and diesel-range alkanes (C5–C22) accounted for 77.1 wt% of the products. Additionally, the catalyst demonstrated excellent performance with real-world single-use polyolefin products. This work provides a new approach for controlling intermediate adsorption in polyolefin recycling, offering a promising path to enhance the efficiency and selectivity of plastic recycling technologies.

Stable isotope labeling LC–MS for profiling the amine submetabolome in a D-lactate treated cell model

Yue-qiang Chen,Xiao-xia Dong,Li Liu,Xiu-ping Chen,Chen-guo Feng,Li-xing Zhan,Yue Su,Fang Zhang,Yin-long Guo

Background Alterations in the amine submetabolome are closely associated with cellular metabolic status and are important for understanding metabolic regulation under intervention conditions. In this study, a stable isotope labeling derivatization combined with liquid chromatography–mass spectrometry (LC–MS) was employed to characterize alterations in the cellular amine submetabolome. Optimization of chromatographic separation and cellular metabolic quenching procedures improved the separation performance of amine metabolites while enabling more accurate preservation of the metabolic state at the time of sampling. Results The established method was applied to a D-lactate–treated BEAS-2B cell model to evaluate amine submetabolome alterations under different compound intervention conditions. The results demonstrated that selenomethionine (SeMet) and berberine alleviated D-lactate induced abnormalities in the amine submetabolome and showed metabolic regulatory effects consistent with tumor-suppressive trends observed under in vivo experiments. Significance Overall, this analytical strategy enables characterization of the amine submetabolome in complex biological samples and provides a reliable methodological reference for metabolome-based investigations of cellular metabolic alterations.

Assessment of p-Xylene Migration Behaviour in Unsaturated Soil Systems: A 3-D Sand Flow Chamber Study

The influence of soil water content and contaminant injection pressure on the migration behaviour of p-Xylene (one of the organic pollutants in Benzene Toluene Ethylbenzene & Xylene) is investigated in the unsaturated zone using the controlled laboratory sandbox experiments. The results show that, at equivalent migration distances, higher soil water content leads to longer migration durations and reduces transport velocities, whereas greater injection pressure promotes faster contaminant movement. These findings highlight the governing role of water saturation in the water–oil–gas three-phase system, in which increased water content decreases the relative permeability of the oil phase and retards capillary-driven BTEX transport. Unlike many previous studies in which contaminants commonly migrate downward toward the groundwater table, the BTEX in this study did not reach the water table and exhibited partial upward migration. Overall, the results provide experimental-scale insight into key mechanisms governing BTEX transport in unsaturated sandy media and serve as a reference for improving predictions of contaminant fate and migration pathways in field settings.

Shape-Induced d-Band Center Optimization of PdBiNi Nanocubes for Exclusive Oxidation of Glycerol into C3 Products

Zeng Qing,Tamtaji Mohsen,Zhou Rui,Zhou Tao,Guo Zhengxiao,Chen GuanHua,Tse Edmund C. M.

Electrocatalytic oxidation of glycerol toward high-value C3 products on Pd-based catalysts presents a promising strategy for upgrading and converting glycerol. However, C3 intermediates often adsorb too tightly on Pd-based catalyst surfaces during glycerol oxidation, leading to C–C bond cleavage. Herein, cubic-shaped PdBi nanoparticles with tunable Ni doping levels are successfully synthesized through a one-step solvothermal method. Owing to the downshift of d-band center originating from the introduction of Bi and Ni as well as the cubic shape, the PdBiNi ternary nanocubes (NCs) exhibit excellent electrocatalytic performance for the glycerol oxidation reaction (GOR). Specifically, Pd 83 Bi 12 Ni 5 NCs with the lowest d-band center exhibit a specific activity of 61.12 mA cm geo –2 and a mass activity of 5.34 A mg Pd –1 . Notably, the Faradaic efficiency (FE) toward C3 products exceeds 97%. In situ Fourier transform infrared spectroscopy and density functional theory calculations show that key C3 intermediates are easily desorbed from the catalyst surface, thereby suppressing C–C bond cleavage and thus preventing overoxidation into low-value products. In addition, Pd 83 Bi 12 Ni 5 NCs possess long-term durability over the course of 16 cycles (1 h/cycle) with an FE for C3 products between 92.5% and 97.6% upon scale-up deployment in a flow electrolyzer, validating its feasibility in practical operations.

Elevating the d-Band Center of Ni3S2 Nanosheets by Fe Incorporation to Boost the Oxygen Evolution Reaction

Jie Ying,Zhen-Zhao He,Jiang-Bo Chen,Yu-Xuan Xiao,Xiao-Yu Yang

Many attempts have been made to enhance the relatively poor electrochemical activity of Ni3S2 for the oxygen evolution reaction (OER) by elevating the d-band center. Unfortunately, only limited success has been encountered thus far. Owning to the lower electronegativity and one less 3d electron relative to Ni, Fe shows great potentials in upshifting the overall d-band center of Ni3S2 when incorporating into its crystal structures. Herein, to enhance the intrinsic activity by elevating the d-band center, Ni3S2 nanosheets incorporated with suitable Fe content have been fabricated by a facile one-step solvothermal method. The obtained Fe-incorporated Ni3S2 catalyst exhibits an outstanding OER performance in alkaline media, only requiring 244 mV overpotential (with a reduction of 210 mV compared to Ni3S2) at 50 mA cm–2 in 1 M KOH and without obvious degradation after sustaining for a 60 h test at a voltage above 1.5 V. Ultraviolet photoemission spectroscopy and density functional theory calculations consistently demonstrate that the superior performance of Fe-incorporated Ni3S2 is attributed to the upshift of the d-band center on neutralizing the electron densities of Ni, which optimize greatly the adsorption energy of the intermediate (OOH*) in the rate-determining Volmer step.

Cloning and functional analysis of 1-deoxy-d-xylulose-5-phosphate synthase (DXS) in Santalum album L

Xiaohong Chen,Yueya Zhang,Haifeng Yan,Meiyun Niu,Yuping Xiong,Xinhua Zhang,Yuan Li,Jaime A. Teixeira da Silva,Guohua Ma

The commercial value of Santalum album L. lies in its aromatic heartwood and essential oil. Sesquiterpenes are the main components of sandal essential oil, and these are synthesized through the plant’s mevalonate (MVA) and methylerythritol phosphate (MEP) pathways. In this study, the first key rate-limiting enzyme, 1-deoxy- d -xylulose-5-phosphate synthase (SaDXS), was investigated to provide a theoretical molecular basis for the sandalwood MEP sesquiterpene biosynthetic pathway. The biofunctions of SaDXS were also analyzed. SaDXS promoters were successfully cloned from a seven-year-old S. album tree. SaDXS1A/1B promoter activity was verified by a β-glucuronidase (GUS) assay and by analyzing cis -acting elements of the promoters, which carried light- and methyl jasmonate (MeJA)-responsive signals. In an experiment involving yellow S. album seedlings, exposure to light upregulated SaDXS1A/1B expression and increased chlorophyll and carotenoid contents when overexpressed in Arabidopsis thaliana . Analysis of the expression of SaDXS1A/1B and SaSSy , key genes of santalol biosynthesis, revealed SaDXS1A expression in all tissues whereas SaDXS1B was expressed in tissues that contained photosynthetic pigments, such as stems, leaves and flowers. Sandal seedlings exogenously treated with two hormones, MeJA and ethylene, revealed similar expression patterns for SaDXS1A/1B and SaSSy . Sandal seedlings were treated with an inhibitor of DXS, clomazone, but showed no significant changes in the contents of α-santalene, β-santalene and α-santalol between treatment and control groups. These results suggest that SaDXS1A/1B play a role in the synthesis of sandalwood sesquiterpenes, providing carbon for downstream secondary metabolites. SaDXS1A/1B also play a role in the biosynthesis of chlorophyll, carotenoids, and primary metabolites.

Highly stable nanostructured lipid carriers containing candelilla wax for d-limonene encapsulation: Preparation, characterization and antifungal activity

Xin Wang,Jiayi Sun,Shenghan Zhao,Fang Zhang,Xianghong Meng,Bingjie Liu

The objective of this work was to develop nanostructured lipid carriers (NLCs) with preservation effect by using pea protein isolate (PPI) nanoparticles as emulsifiers, candelilla wax (CW) as organo-gelator and d -limonene (DL) as antifungal agent. The optimal formulation parameters of NLCs were firstly determined based on results of particle size, poly-dispersity index and zeta potential, and then NLCs prepared by optimal formulation were further characterized. The results showed that DL was successfully encapsulated inside NLCs. Moreover, the encapsulation of amorphous DL led to more disordered crystalline state of NLCs. In addition, in comparing the properties of NLCs and nanoemulsions (NEs) without CW, it was found that the addition of CW seemed to have several beneficial effects on NLCs: 1) NLC droplets were well dispersed, whereas NE droplets exhibited coalescence and flocculation; 2) compared with NEs, NLCs displayed excellent storage stability and inhibition ability of DL release. Furthermore, antifungal activity of NLCs was observed by in vitro and in vivo study. The acquired information in current research can provide novel insight into development of stable and antifungal nanocarriers that own a promising application in tomato preservation.

Transition-metal-free decarboxylation of D-glucaric acid to furan catalyzed by SnCl4 in a biphasic system

Teng Li,Guangyu Sun,Lu Xiong,Boying Zheng,Yaqi Duan,Rui Yu,Jun Jiang,Yantao Wang,Weiran Yang

As a useful chemical, furan can be produced from bio-based chemicals, such as furfural and furoic acid (FA). There were few reports on the preparation of furan from bio-based C6 aldaric acids . Herein, a new method was developed to produce furan from D-glucaric acid (GA) without transition metals, and nearly 80% yield of furan was produced in the water/toluene biphasic system with SnCl 4 at 200 °C in 2 h. 3-Hydroxy-2-pyrone (3-HP) and FA were proved to be the key intermediates in the formation of furan from GA, and the reaction pathway was proposed to be GA→ 3-HP→ FA→ furan based on the kinetic study , model substrate reaction, and isotope labeling experiments. SnCl 4 gave the highest furan yield among the common acid catalysts, and the contrast experiments suggested that H + , Cl − and Sn 4+ all have promoting effect on GA conversion to furan. This method was also applicable with other C6 aldaric acids.

Electrodeposition of paracetamol oxide for intelligent portable ratiometric detection of nicotine and ethyl vanillin β-D-glucoside

Zhaohong Su,Shiyu Hu,Yuhang Zhang,Zhanning Liang,Yi Peng,Qinyi Cao,Xia Yu,Zhiyang Zhu,Pei He,Zhenjie Li

Herein, the electrodeposition of paracetamol oxide (PA ox) for the intelligent portable ratiometric detection of nicotine (NIC) and ethyl vanillin β-D-glucoside (EVG) is reported. PA ox electrodeposited on a screen-printed carbon electrode (SPCE) was used as a new fixed state ratiometric reference probe. A portable electrochemical workstation combined with a smart phone was applied as an intelligent portable electrochemical sensing platform. The sensor was studied by scanning electron microscopy (SEM), Fourier transform infrared spectrophotometry (FT-IR), ultraviolet-visible spectrophotometry (UV-vis), theoretical calculation, chronoamperometry, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV). Under optimized conditions, the detection range of NIC is 10–200 μmol L−1, and the detection limit is 0.256 μmol L−1. The detection range of EVG was 10–180 μmol L−1, and the detection limit was 0.058 μmol L−1. The sensor can realize the real-time detection of NIC and EVG concentration in cigarette samples quickly and accurately, and has good anti-interference, repeatability and stability.

Hole-rich CoP nanosheets with an optimized d-band center for enhancing pH-universal hydrogen evolution electrocatalysis

Shuo Geng,Fenyang Tian,Menggang Li,Xin Guo,Yongsheng Yu,Weiwei Yang,Yanglong Hou

Tailoring the d-band center is an effective method to promote the hydrogen evolution reaction (HER) activity of electrocatalysts. Herein, we demonstrate that the d-band center can be tuned through a hole-creating method to enhance pH-universal HER activity using CoP as a basic platform. The density functional theory (DFT) calculation reveals that the d-band center and the valence electron number of Co sites around the holes are upshifted, which boosts H adsorption. In addition, introducing holes into the nanosheets of CoP can optimize the ΔGH* of the Co atoms around the holes. Inspired by the DFT results, a soft template method was developed to synthesize hole-rich CoP nanosheets. With the advantages of hole-rich and unique nanosheet features, the hole-rich CoP nanosheets show low HER overpotentials with only 84 and 94 mV to achieve a current density of 10 mA cm−2 in both acidic and alkaline media, better than that of the other dimensional counterparts. In addition, the hole-rich CoP nanosheets also show satisfactory stability after long-term HER tests. This strategy of regulating the d-band center is expected to be extended to other transition metal phosphide electrocatalysts for enhancing the HER performance.