Amorphous Nanoparticles Research Articles

S−S Bond Strategy at Sulfide Heterointerface: Reversing Charge Transfer and Constructing Hydrogen Spillover for Boosted Hydrogen Evolution

AbstractDeveloping efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuSx/NbS2, which is composed of 3R‐type NbS2 loaded by amorphous RuSx nanoparticles with S−S bonds formed at the interface. As HER electrocatalyst, the RuSx/NbS2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm−2 in acid, and also low Tafel slope of 51.05 mV dec−1. The intrinsic activity of RuSx/NbS2 is much higher than that of Ru/NbS2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS2 to RuSx that driven by the formation of S−S bonds, resulting in electron‐rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS2. This study provides an effective S−S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications.

Low-Temperature Synthesis of GeTe Nanoparticles.

Nanoparticles can offer an alternative approach to fabricate phase-change materials. The chemical synthesis of GeTe nanoparticles using organometallic precursors exploits high-boiling solvents and relatively high temperatures (close or even above crystallization temperatures), as reported in the available literature. The aim of this work is the preparation of GeTe nanoparticles by a low-temperature synthetic method exploiting new organometallic precursors and common organic solvents. Indeed, different preparation methods and characterization of GeTe nanoparticles is discussed. The characterization of the prepared nanomaterial was performed on the basis of X-ray diffraction, transmission electron microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, laser ablation time-of-flight mass spectrometry, Raman scattering spectroscopy, and dynamic light scattering. The results show that the low-temperature synthetic route leads to amorphous GeTe nanoparticles. Exploited organometallic precursor is stabilised by neutral ligand which can be isolated after the reaction and repeatedly used for further reactions. Furthermore, GeTe nanoparticle size can be tuned by the conditions of the synthesis.

Partially Amorphous Ru-Doped CoSe Nanoparticles with Optimized Intermediates Adsorption for Highly Efficient Sulfur Oxidation Reaction.

The application of thermodynamically more favorable sulfur oxidation reaction (SOR) to replace oxygen evolution reaction (OER) in electrocatalytic water electrolysis is an appealing strategy to achieve low-energy hydrogen production while removing toxic sulfur ions from wastewater. However, the study of SOR catalysts with both activity and stability still faces great challenges. Herein, this study prepares partially amorphous Ru-doped CoSe (pa-Ru-CoSe) nanoparticles for SOR. The doping of Ru keeps Co in an electron-deficient state, which enhances the adsorption of SOR intermediates and improves the catalytic activity. Meanwhile, the partially amorphous selenide possesses great corrosion resistance to sulfur species, thus ensuring stability in long-term SOR. In addition, the pa-Ru-CoSe requires only 0.566V to reach a current density of 100mA cm-2 in the SOR-HER coupled system and remains stable for 200 h. This work provides a promising partially amorphous strategy for SOR catalysts with both catalytic activity and long-term stability, enabling hydrogen production with low energy consumption and simultaneous sulfur production.

Setting reaction of a olivine-based Mg-phosphate cement

The cementitious properties of natural Mg-rich olivine when reacted with a phosphoric acid solution are investigated, as a function of acid concentration and liquid/solid mass ratio. The obtained cements are composed of residual olivine crystals and amorphous silica nanoparticles dispersed in a dense and compact newberyite (MgHPO4∙3H2O) matrix. The latter was mostly formed by packed micrometric tabular crystals, although evidence of the presence of a fraction of amorphous MgHPO4 was also found. Water content in the raw mix was observed to play a pivotal role on the reaction pathway, either promoting porosity or hindering the crystallization of the products. Up to 57 % of olivine reactivity, whose dissolution was promoted by the curing temperature (60 °C) and low pH, was achieved. All in all, these results indicate that the industrial mineral olivine may serve a viable source of Mg for the production of phosphate cements.

Tuning the crystallinity of Cu-based electrocatalysts: Synthesis, structure, and activity towards the CO2 reduction reaction

The rising levels of CO2 have spurred growing concerns for our environment, and curbing CO2 emissions may not be practically viable with the expanding human population. One attractive strategy is the electrochemical CO2 reduction (CO2RR) into value added chemicals but because of the chemical inertness of the CO2 molecule, the electrochemical reduction requires a suitable catalyst. Cu-based catalysts have been largely investigated for CO2RR, however, the difficulty achieving a high selectivity and faradaic efficiency towards specific products, especially hydrocarbons, is still a challenge, alongside the concern over cost, stability and scarcity of the metal catalyst. The present research focuses on tuning the crystallinity of Cu nanoparticles via a green, cost-friendly, and facile method, called the urea glass route. Remarkably, the incorporation of a selected nitrogen-carbon rich source (namely, 4,5 dicyanoimidazole) at low temperatures allow the formation of an oxidized derived amorphous Cu system, whilst a second thermal treatment enables the transformation to crystalline Cu0. We found that the combination of surface Cu0 and Cu1+ (observed via XPS studies) present in our amorphous and crystalline Cu nanoparticles leads to interesting differences in the final catalytic activity when tested under CO2 reaction conditions. The combination of extended X-ray absorption fine structure (EXAFS) experiments and molecular dynamics simulations provides compelling evidence for the amorphous and metallic nature of Cu nanoparticles.

Size-Dependent Core-Shell Fine Structures and Oxygen Evolution Activity of Electrochemical IrOx Nanoparticles Revealed by Cryogenic Electron Microscopy.

Electrochemically oxidized amorphous iridium oxides (IrOx) offer significantly improved electrocatalytic activities on the oxygen evolution reaction (OER) compared to crystalline IrO2, yet the origin of their decent activity and their size-dependent properties have not been fully understood. An important argument is the formation of deprotonated oxygen species not only at the topmost surface but also at the near surface, which creates an electrophilic character that activates the OER electrocatalysis. However, high spatial resolution identification of the electrophilic oxygen species remains unachieved. We address this hitherto-unresolved problem on size-selected electrochemical IrOx nanoparticles (NPs) by using cryogenic scanning transmission electron microscopy combined with electron energy loss spectroscopy, which enables simultaneous atomic detection of the near surface compositional and electronic structures with minimal damage that are further correlated with their size-dependent OER activities. Depending on the particle size, the electrochemical IrOx NPs showed distinctly different core-shell fine structures ranging from amorphous and hydrous IrOxHy NPs to a "metallic Ir core/sub-stoichiometric IrOx interlayer/amorphous IrOxHy shell" NP structure. Moreover, the formation of deprotonated, electrophilic oxygen is directly identified at the substoichiometric IrOx interface layer. These features account for a previously unestablished particle size effect of the electrochemical IrOx NPs, showing increasing water oxidation reactivity with an increasing nanoparticle size. Our results provide important insights into how subsurface oxygen chemistry controls the surface reactivity in the nanoscale Ir-based OER electrocatalysts.

Scale-up and clinical bioavailability assessment of a 45 % drug loaded amorphous nanoparticle formulation of a BCS IV compound for oral delivery

A 45 % drug loaded (DL) amorphous nanoparticle (ANP) formulation for a BCS IV drug demonstrated promising pharmacokinetics in dogs (Purohit, et al., J. Pharm. Sci. 2023(113)1007–1019). This preclinical data enabled a human proof-of-concept assessment opportunity. The ANP freeze dried powder for oral suspension was prepared using solvent/antisolvent precipitation followed by organic solvent removal and freeze drying (FD). Challenges manifested during scale-up from 50 g to 280 g. Given the preclinical data, formulation change was restricted, therefore, process modifications were implemented. Cold collection after precipitation prevented particle growth but resulted in 75 nm particles at clinical scale (CS), compared to 150 nm at laboratory scale (LS). This size decrease rendered stabilizer amounts suboptimal for FD operation. Consequently, when FD powder was resuspended in water a smaller fraction of particles was below 450 nm (by filtration), ∼65 % for CS compared to ∼85 % for LS. Formulation was stable for > 6 months, evaluated by monitoring moisture content, assay, powder X-ray diffraction (PXRD), and redispersion time. Despite ∼65 % re-dispersibility, this 45 % DL formulation in humans had higher Cmax and AUC ∼73 % and ∼46 % respectively in fasted-state, and under fed-state it met bioequivalence criteria for AUC but Cmax was 20 % lower compared to reference (10 % DL ASD tablets) demonstrating advantage of ANP strategy over ASD approach.

Designing of amiloride loaded citrate functionalized amorphous silica nanoparticles to investigate its genotoxic and cytotoxic potential

In the present work, silica-based nanocarrier for the anticancer drug, amiloride have been synthesized and characterized using various physicochemical techniques. The aim of this work emphasis on investigating the physicochemical properties and cytotoxic effects of citrate-functionalized amiloride loaded silica nanoparticles. Silica nanoparticles synthesis was carried out via condensation reaction, then coated by tris sodium citrate, followed by their functionalization using amiloride through EDC-NHS reaction. SEM and HR-XRD analysis indicated the formation of amorphous spherical silica nanoparticles. The existence of citrate coating was evident from FT-IR and TGA results, which were supported by DLS and zeta potential studies. The formation of amiloride conjugated citrate coated silica nanoparticles (SiNPs-Cit@Ami) was confirmed by the DLS, Zeta potential and UV-Visible spectroscopy. Size of SiNPs-Cit@Ami nanoparticles was found to be around 80nm using TEM. Additionally, these nanoparticles showed high loading efficiency and time-dependent release of amiloride. DNA binding studies were examined using UV–Visible, Fluorescence spectroscopic and Competitive fluorescence studies. The results indicate that SiNPs-Cit@Ami bind to Ct-DNA via minor groove binding mode. Furthermore, the cytotoxic effect of SiNPs-Cit@Ami on HepG2 cell lines was found to be higher than amiloride alone. Our findings suggest that SiNPs-Cit@Ami can be employed as a promising candidate for cancer mitigation.

Plasma assisted single-step synthesis of carbon-coated SrFe2O4 electrodes for enhancing supercapacitor and oxygen evolution reaction

Developing highly efficient, conductive, and porous electrode materials for superior electrochemical bifunctional applications presents a formidable challenge, particularly when considering impurity-free large-scale production. This investigation focuses on synthesizing a composite material of highly conductive amorphous carbon-coated SrFe2O4 nanoparticles to enhance supercapacitor and oxygen evolution performance. The C@SrFe2O4 nanoparticles were synthesized through a thermal plasma process utilizing argon, methane, and carbon dioxide gas environments. The prepared samples' phase, crystal structure, morphology, elemental composition, and chemical state analysis were thoroughly examined. The electrochemical performance of the prepared samples, including Fe3O4, SrO, and C@SrFe2O4 electrodes, was evaluated for their suitability in electrochemical capacitor applications. Remarkably, C@SrFe2O4 nanoparticles exhibited notable electrochemical pseudocapacitive behavior, demonstrating a significantly higher specific capacitance of 588.7 F/g at a current density of 1 A/g. Moreover, at a current density of 10 A/g, the C@SrFe2O4 electrode exhibited outstanding cycling stability, maintaining 91 % of its initial capacitance over 5000 charge-discharge cycles. Furthermore, it showcased exceptional and uniform electrocatalytic activity for the OER, requiring only 186 mV in overpotentials to achieve a current density of 10 mA/ cm2. These findings underscore the potential of mesoporous C@SrFe2O4 nanoparticles as promising materials for supercapacitors and OER applications.

Synthesis, characterization, and biological properties of calcium and zinc based ION incorporated amorphous carbonate nanoparticles

In this study, magnesium (Mg), zinc (Zn), and strontium (Sr) incorporated amorphous calcium carbonate (ACC) nanoparticles were synthesized. Results revealed that at low Zn concentrations, Zn and Sr co-incorporated, Mg-stabilized amorphous calcium carbonate (ACMC) nanoparticles were obtained. However, at high Zn concentrations, instead of ACMC, calcium (Ca) and Sr co-incorporated, magnesium-stabilized amorphous zinc carbonate (AZMC) nanoparticles were obtained. Our results demonstrated that Mg could be used to stabilize the amorphous structure of both nanoparticles. The additive ions could be incorporated into the structure of both ACMC and AZMC without impairing their amorphous nature. The synthesized nanoparticles had an average size of about ∼30 nm. Degradation studies suggested that the degradation rate of AZMC nanoparticles could be slower compared to ACMC nanoparticles. Antibacterial tests showed that the number of colony forming units for the Ca and Sr co-incorporated AZMC nanoparticles was lower for both Staphylococcus aureus (S. aureus), and Escherichia coli (E. coli) strains compared to the control group. Cytotoxicity studies revealed that fibroblasts interacting with the ion-incorporated ACMC and AZMC nanoparticles remained viable and proliferated for up to 5 days in vitro. These results demonstrated for the first time that Zn and Sr co-incorporated ACMC nanoparticles were non-toxic, biodegradable, and possessed antibacterial properties. In addition, Ca and Sr co-incorporated AZMC nanoparticles exhibited a stronger antibacterial effect, which makes them promising candidates for antibacterial applications.

Sensitive Electrochemical Sensing Properties for Cyanide Detection Using Polyaniline/Cu-Vanadate Nanobelt-modified Electrode

Background: Cyanide is a toxic anion and may be discarded into the water environment, which is a serious threat to human beings and the environment. Hence, it is essential to explore a facile, sensitive method for cyanide detection. Polyaniline/Cu vanadate nanobelts serve as electrode materials for sensitive cyanide determination. Methods: Polyaniline/Cu vanadate nanobelts were obtained by a simple route using polyaniline, Cu vanadate nanobelts. The polyaniline/Cu vanadate nanobelts were measured via electron microscopy, diffraction, infrared spectrum, and electrochemical methods. Results: Amorphous polyaniline nanoparticles with a particle size of about 100 nm were attached firmly to the surface of Cu vanadate nanobelts. Electrochemical sensing properties for cyanide detection were analyzed using a cyclic voltammetry technique using the nanobelts-modified electrode. The cyclic voltammograms (CV) peaks centered at +0.64 V and +0.54 V were observed using the polyaniline/Cu vanadate nanobelts in 0.1 M KCl solution with 2 mM cyanide. The proposed composite nanobelt-modified electrode possessed the detection range and detection limit of 0.001-2 mM and 0.22 μM, respectively. Conclusion: Polyaniline greatly enhances the electro-catalytic performance of the Cu vanadate nanobelt-modified electrode for cyanide detection.

Characterization and biological activity of selenium nanoparticles biosynthesized by Yarrowia lipolytica.

In this research, biogenic selenium nanoparticles were produced by the fungi Yarrowia lipolytica, and the biological activity of its nanoparticles was studied for the first time. The electron microscopy analyses showed the production of nanoparticles were intracellular and the resulting particles were extracted and characterized by XRD, zeta potential, FESEM, EDX, FTIR spectroscopy and DLS. These analyses showed amorphous spherical nanoparticles with an average size of 110 nm and a Zeta potential of -34.51 ± 2.41 mV. Signatures of lipids and proteins were present in the capping layer of biogenic selenium nanoparticles based on FTIR spectra. The antimicrobial properties of test strains showed that Serratia marcescens, Klebsiella pneumonia, Escherichia coli, Pseudomonas aeruginosa and Bacillus subtilis were inhibited at concentrations between 160 and 640 μg/mL, while the growth of Candida albicans was hindered by 80 μg/mL of biogenic selenium nanoparticles. At concentrations between 0.5 and 1.5 mg/mL of biogenic selenium nanoparticles inhibited up to 50% of biofilm formation of Klebsiella pneumonia, Acinetobacter baumannii, Staphylococcus aureus and Pseudomonas aeruginosa. Additionally, the concentration of 20-640 μg/mL of these bioSeNPs showed antioxidant activity. Evaluating the cytotoxicity of these nanoparticles on the HUVEC and HepG2 cell lines did not show any significant toxicity within MIC concentrations of SeNPs. This defines that Y. lipolytica synthesized SeNPs have strong potential to be exploited as antimicrobial agents against pathogens of WHO concern.

Synthesis of Amorphous and Various Phase-Pure Nanoparticles of Nickel Phosphide with Uniform Sizes via a Trioctylphosphine-Mediated Pathway.

Nickel phosphides are of particular interest because they are highly active and stable catalysts for petroleum/biorefinery and hydrogen production. Despite their significant catalytic potential, synthesizing various phase-pure nickel phosphide nanoparticles of uniform size remains a challenge. In this work, we develop a robust trioctylphosphine (TOP)-mediated route to make highly uniform phase-pure Ni12P5, Ni2P, and Ni5P4 nanoparticles. The synthetic route forms amorphous Ni70P30 nanoparticle intermediates. The reactions can be stopped at the amorphous stage when amorphous particles are desired. The amount of P incorporation can be controlled by varying the ratio of TOP to Ni(II). The mechanism for composition control involves the competition of the kinetics of two processes: the addition of the reduced Ni and the incorporation of P into Ni. Uniform Ni70P30 amorphous nanoparticles can be generated at a high TOP-to-Ni(II) ratio, where the P incorporation kinetics is made to dominate. Ni70P30 can later be transformed into phase-pure Ni12P5, Ni2P, and Ni5P4 nanocrystals of uniform size. The transformation can be controlled precisely by modulating the temperature. A UV-vis study coupled with theoretical modeling reveals Ni(0)-TOPx complexes along the synthetic path. This approach may be expanded to create other metal compounds, potentially enabling the synthesis of uniform nanoparticles of a greater variety.

Heteroatoms-Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation.

As a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over-hydrogenation. Herein, we develop an efficient catalytic system based on single-atom Pd catalysts supported on boron-containing amorphous zeolites (Pd/AZ-B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ-B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h-1 and demonstrating 95 % selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom-free amorphous zeolite-anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73 % and 15 %, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.

A FAPα-activated MRI nanoprobe for precise grading diagnosis of clinical liver fibrosis

Molecular imaging holds the potential for noninvasive and accurate grading of liver fibrosis. It is limited by the lack of biomarkers that strongly correlate with liver fibrosis grade. Here, we discover the grading potential of fibroblast activation protein alpha (FAPα) for liver fibrosis through transcriptional analysis and biological assays on clinical liver samples. The protein and mRNA expression of FAPα are linearly correlated with fibrosis grade (R2 = 0.89 and 0.91, respectively). A FAPα-responsive MRI molecular nanoprobe is prepared for quantitatively grading liver fibrosis. The nanoprobe is composed of superparamagnetic amorphous iron nanoparticles (AFeNPs) and paramagnetic gadoteric acid (Gd-DOTA) connected by FAPα-responsive peptide chains (ASGPAGPA). As liver fibrosis worsens, the increased FAPα cut off more ASGPAGPA, restoring a higher T1-MRI signal of Gd-DOTA. Otherwise, the signal remains quenched due to the distance-dependent magnetic resonance tuning (MRET) effect between AFeNPs and Gd-DOTA. The nanoprobe identifies F1, F2, F3, and F4 fibrosis, with area under the curve of 99.8%, 66.7%, 70.4%, and 96.3% in patients’ samples, respectively. This strategy exhibits potential in utilizing molecular imaging for the early detection and grading of liver fibrosis in the clinic.

Amorphization-sparked superb activity and excellent coke-resistance of Ni nanocatalyst

Selective conversion of CH4 and CO2 to syngas via the dry reforming reaction is highly desirable in terms of restraining the greenhouse effect and meanwhile acquiring useful chemicals. However, the most promising Ni catalysts for the reaction still suffer from severe coking and thus poor durability. Here, we report that using amorphous Ni nanoparticles synthesized on an N modified mesoporous silica support, the catalytic activity and coke-resistant performance of Ni toward the photothermal dry reforming of methane (DRM) are greatly improved. Theoretical calculations further unveil that the amorphous Ni nanoparticles are much more energetically favorable to activate the CH4 and CO2 molecules as well as to remove the C* intermediates for coke formation than their crystalline Ni counterparts, which renders the amorphous Ni nanoparticles with both superb activity and excellent coke-resisting property. This finding possibly provides a new avenue to make both highly efficient and anti-coking catalysts for the DRM reaction and beyond via facile amorphization of active metals.

Amorphous silica nanoparticles exhibit antitumor activity in triple-negative breast cancer cells.

Triple-negative breast cancer (TNBC) is an aggressive subtype of breast cancer that is mainly treated with cytotoxic chemotherapy. However, this treatment is not always effective, and an important percentage of patients develop recurrence. Nanomaterials are emerging as alternative treatment options for various diseases, including cancer. This work reports the synthesis, characterization, antitumor activity evaluation, and sub-acute toxicity studies of two formulations based on amorphous silica nanoparticles (SiNPs). They are functionalized with 3-aminopropyltriethoxisilane (Si@NH2) and folic acid (FA; Si@FA). The results show that SiNPs reduce the viability and migration of TNBC MDA-MB-231 and 4T1 cell lines and Si@FA do not affect the growth of the mammary nonmalignant HC11 cells. In addition, Si@FA induces reactive oxygen species (ROS) generation and displays antiproliferative and subsequently proapoptotic effects in MDA-MB-231 cells. Moreover, none of the SiNPs cause signs of sub-acute toxicity in mice when administered at 30 mg/kg over a month. In conclusion, these nanosystems display intrinsic antitumor activity without causing toxic in vivo effects, being a promising therapeutic alternative for TNBC.

Outbreak simulation on the neonatal ward using silica nanoparticles with encapsulated DNA: unmasking of key spread areas

Nosocomial infections pose a serious threat. In neonatal intensive care units (NICUs) in particular, there are repeated outbreaks caused by microorganisms without the sources or dynamics being conclusively determined. This study aims to use amorphous silica nanoparticles with encapsulated DNA (SPED) to simulate outbreak events and to visualize dissemination patterns in a NICU to gain a better understanding of these dynamics. Three types of SPED were strategically placed on the ward to mimic three different dissemination dynamics among real-life conditions and employee activities. SPED DNA, resistant to disinfectants, was sampled at 22 predefined points across the ward for four days and qPCR analysis was conducted. Starting from staff areas, a rapid ward-wide SPED dissemination including numerous patient rooms was demonstrated. In contrast, a primary deployment in a patient room only led to the spread in the staff area, with no distribution in the patient area. This study pioneers SPED utilization in simulating outbreak dynamics. By unmasking staff areas as potential key trigger spots for ward-wide dissemination the revealed patterns could contribute to a more comprehensive view of outbreak events leading to rethinking of hygiene measures and training to reduce the rate of nosocomial infections in hospitals.

S-S Bond Strategy at Sulfide Heterointerface: Reversing Charge Transfer and Constructing Hydrogen Spillover for Boosted Hydrogen Evolution.

Developing efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuSx/NbS2, which is composed of 3R-type NbS2 loaded by amorphous RuSx nanoparticles with S-S bonds formed at the interface. As HER electrocatalyst, the RuSx/NbS2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm-2 in acid, and also low Tafel slope of 51.05 mV dec-1. The intrinsic activity of RuSx/NbS2 is much higher than that of Ru/NbS2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS2 to RuSx that driven by the formation of S-S bonds, resulting in electron-rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS2. This study provides an effective S-S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications.

Effects of foliar treatments with urea and nano-urea on the cell walls of Monastrell grape skins

Cell wall composition can be affected by nitrogen availability in the vineyard. Foliar application of urea is effective in supplying nitrogen needs and increasing the nitrogen content of musts. Due to the low recoveries of urea fertilisation, more effective application methods such as the use of nanotechnology are needed. In this work, the effect on the composition of Monastrell grape skin cell walls, after foliar application of urea and amorphous calcium phosphate nano-particles doped with urea was studied. The treatments with urea and nano-urea, although the urea content in the nano-treatment was eight times lower than in the conventional treatment, produce an equivalent modification of the cell wall. In fact, both treatments produced an increase in cell wall thickness and in cell wall composition, contents of proteins, hemicellulose and uronic acids also increased. However, phenolic compounds were not affected and cellulose showed lower concentrations than control grapes. Regarding the spectrophotometric parameters of the wine studied, the anthocyanins content and colour intensity were reduced in wines with both treatments and the total polyphenol index was slightly affected.