Synthesis of PtNi Nanoparticles to Accelerate the Oxygen Reduction Reaction.

We report the synthesis of core-shell Ni-Pt nanoparticles (NPs) with varying degrees of crystallographic facets and surface layers rich in Pt via a seed-mediated thermolytic approach. Mixtures of different surfactants used during synthesis resulted in preferential surface passivation, which in turn dictated the size, chemical composition, and geometric evolution of these PtNi NPs. Electrochemical investigations of these pristine core-shell Ni-Pt structures in the oxygen reduction reaction (ORR) show that their catalytic functionalities outperform the commercial Pt/C reference catalyst. The enhanced electrocatalytic ORR performances of these Pt-based PtNi NPs are correlated with the weakened oxygen binding strength or surface-adsorbed hydroxyl (OH) species on active Pt surface sites induced by the downshift of the d-band center as a result of compressive strain effects. Our studies offer a robust synthetic approach for the development of core-shell nanostructures for enhanced ORR catalysis.

Room Temperature Ion Beam Synthesis of Ultra-Fine Molybdenum Carbide Nanoparticles: Toward a Scalable Fabrication Route for Earth-Abundant Electrodes.

Molybdenum carbides are promising low-cost electrocatalysts for electrolyzers, fuel cells, and batteries. However, synthesis of ultrafine, phase-pure carbide nanoparticles (diameter < 5 nm) with large surface areas remains challenging due to uncontrollable agglomeration that occurs during traditional high temperature syntheses. This work presents a scalable, physical approach to synthesize molybdenum carbide nanoparticles at room temperature by ion implantation. By tuning the implantation conditions, various molybdenum carbide phases, stoichiometries, and nanoparticle sizes can be accessed. For instance, molybdenum ion implantation into glassy carbon at 30 keV energy and to a fluence of 9 × 1016 at cm-2 yields a surface η-Mo3 C2 with a particle diameter of (10 ± 1) nm. Molybdenum implantation into glassy carbon at 60 keV to a fluence of 6 × 1016 at cm-2 yields a buried layer of ultrafine γ'-MoC/η-MoC nanoparticles. Carbon ion implantation at 20 keV into a molybdenum thin film produces a 40 nm thick layer primarily composed of ß-Mo2 C. The formation of nanoparticles in each molybdenum carbide phase is explained based on the Mo-C phase diagram and Monte-Carlo simulations of ion-solid interactions invoking the thermal spike model. The approaches presented are widely applicable for synthesis of other transition metal carbide nanoparticles as well.

Facile and Eco-Friendly Approach To Produce Confined Metal Cluster Catalysts.

Zeolite-supported metal nanocluster catalysts have attracted significant attention due to their broad application in heterogeneously catalyzed reactions. The preparation of highly dispersed metal catalysts commonly involves the use of organic compounds and requires the implementation of complicated procedures, which are neither green nor deployable at the large scale. Herein, we present a novel facile method (vacuum-heating) which employs a specific thermal vacuum processing protocol of catalysts to promote the decomposition of metal precursors. The removal of coordinated H2O via vacuum-heating restricts the formation of intermediates (metal-bound OH species), resulting in catalysts with a uniform, metal nanocluster distribution. The structure of the intermediate was determined by in situ Fourier transform infrared, temperature-programmed decomposition, and X-ray absorption spectroscopy (XAS) measurements. This alternative synthesis method is eco-friendly and cost-effective as the procedure occurs in the absence of organic compounds. It can be widely used for the preparation of catalysts from different metal species (Ni, Fe, Cu, Co, Zn) and precursors and is readily scaled-up.

Multifunctional bismuth oxide (Bi2 O3 ) particles: Evidence for selective melanoma therapy.

The current study investigates the therapeutic and optical properties of bismuth oxide (Bi2 O3 ) particles for selective melanoma therapy and prevention. The Bi2 O3 particles were prepared using a standard precipitation method. The Bi2 O3 particles induced apoptosis in human A375 melanoma cells but not human HaCaT keratinocytes or CCD-1090Sk fibroblast cells. This selective apoptosis appears to be associated with a combination of factors: increased particle internalization (2.29 ± 0.41, 1.16 ± 0.08 and 1.66 ± 0.22-fold of control) and enhanced production of reactive oxygen species (ROS) (3.4 ± 0.1, 1.1 ± 0.1 and 2.05 ± 0.17-fold of control) in A375 cells compared to HaCaT and CCD-1090SK cells, respectively. As a high-Z element, bismuth is also an excellent contrast agent for computer tomography, which renders Bi2 O3 a theranostic material. Moreover, Bi2 O3 displays high UV absorption and low photocatalytic activity compared to other semiconducting metal oxides, which opens further potential fields of application as a pigment or as an active ingredient in sunscreens. Overall, this study demonstrates the multifunctional properties of Bi2 O3 particles surrounding the treatment and prevention of melanoma.

Inducing Inorganic Carbon Accrual in Subsoil through Biochar Application on Calcareous Topsoil.

Biochar amendments add persistent organic carbon to soil and can stabilize rhizodeposits and existing soil organic carbon (SOC), but effects of biochar on subsoil carbon stocks have been overlooked. We quantified changes in soil inorganic carbon (SIC) and SOC to 2 m depth 10 years after biochar application to calcareous soil. The total soil carbon (i.e., existing SOC, SIC, and biochar-C) increased by 71, 182, and 210% for B30, B60, and B90, respectively. Biochar application at 30, 60, and 90 t ha-1 rates significantly increased SIC by 10, 38, and 68 t ha-1, respectively, with accumulation mainly occurring in the subsoil (below 1 m). This huge increase of SIC (mainly CaCO3) is ∼100 times larger than the inorganic carbon present in the added biochar (0.3, 0.6, or 0.9 t ha-1). The benzene polycarboxylic acid method showed that the biochar-amended soil contained more black carbon particles (6.8 times higher than control soil) in the depth of 1.4-1.6 m, which provided the direct quantitative evidence for biochar migration into subsoil after a decade. Spectral and energy spectrum analysis also showed an obvious biochar structure in the biochar-amended subsoil, accompanied by a Ca/Mg carbonate cluster, which provided further evidence for downward migration of biochar after a decade. To explain SIC accumulation in subsoil with biochar amendment, the interacting mechanisms are proposed: (1) biochar amendment significantly increases subsoil pH (0.3-0.5 units) 10 years after biochar application, thus forming a favorable pH environment in the subsoil to precipitate HCO3-; and (2) the transported biochar in subsoil can act as nuclei to precipitate SIC. Biochar amendment enhanced SIC by up to 80%; thus, the effects on carbon stocks in subsoil must be understood to inform strategies for carbon dioxide removal through biochar application. Our study provided critical knowledge on the impact of biochar application to topsoil on carbon stocks in subsoil in the long term.

A script-based method for achieving distortion-free selected area electron diffraction.

Electron diffraction patterns obtained on a TEM contain elliptical distortion resulting from column defects. This distortion can be corrected by applying offsets to the objective lens stigmators to cancel distortions occurring further down the column. In this work, a DigitalMicrographTM script-based method has been developed to identify the optimum objective stigmator settings which produce a distortion minimum in diffraction. Initially, a manual (by eye) correction is used to determine the stigmator values necessary to bring the pattern distortion below the threshold at which it is no longer visible to the naked eye (<1%). Thereafter, an automated acquisition script is used to acquire matrices of diffraction patterns while varying the stigmator values about the values which were identified as producing a distortion minimum in the preceding step. This analysis can be applied iteratively to refine the location of the distortion minimum, using progressively finer step changes in objective stigmator values. The optimum stigmator values producing the distortion minimum in diffraction are very different to those in imaging. These imaging and diffraction stigmator values can be saved to script and subsequently recalled at the click of a button, making their application very simple. Using this method, diffraction pattern elliptical distortion in a newly installed TEM was reduced from 1.6% to 0.3%, on a measurement precision of 0.3%, effectively producing distortion-free diffraction. The relevant scripts can be freely downloaded from the internet. RESEARCH HIGHLIGHTS: This paper reports a DigitalMicrograph script-based method to identify and subsequently apply optimized objective stigmator values in diffraction mode. These effectively eliminate elliptical distortion inherent to this diffraction technique.

Biochar-based fertiliser enhances nutrient uptake and transport in rice seedlings.

Biochar-based compound fertilisers (BCF) are gaining increasing attention as they are cost-effectiveness and improve soil fertility and crop yield. However, little is known about the mechanisms by which micron-size BCF particles enhance crop growth. In the present study, Wuyunjing7 rice seedlings were exposed to micron-size particles of wheat straw-based BCF (mBCF) diffused through a 25-µm nylon mesh. The control was fertilised with urea, diammonium phosphate, and potassium chloride to ensure that both treatments received comparables level of N, P, and K. The effects of mBCF on rice seedling growth were evaluated by determining the changes in nitrogen uptake and utilisation via nitrogen content measurements, short-term 15N-NH4+ influx assays, and analyses of transcript-level nutrient transporter gene expression. The shoot biomass of rice seedling treated with mBCF at the rate of 5 mg/ g soil was 33% greater than that for the control. Root and shoot 15N accumulation rates were 44% and 14% higher, respectively, in the mBCF-treated than the control. The mBCF-treated rice seedlings had higher phosphorus, potassium, and iron content than the control. Moreover, the treatments significantly differed in terms of their nutrient transporter gene expression levels. Spectroscopy and microscopy were used to visualise nutrient distributions across transverse root sections. There were relatively higher iron oxide nanoparticle and silicon-based compound concentrations in the roots of the mBCF-treated rice seedlings than in those of the control. The foregoing difference might account for the fact that the growth of the mBCF-treated rice was superior to that of the control. We demonstrated that the mBCF treatment created a more negative electrical potential at the root epidermal cell layer (~ - 160 mV) than the root surface. This potential difference may have been the driving force for mineral nutrient absorption.

Ultra-small cobalt particles embedded in titania by ion beam synthesis: Additional datasets including electron microscopy, neutron reflectometry, modelling outputs and particle size analysis.

This Data-in-brief article includes datasets of electron microscopy, polarised neutron reflectometry and magnetometry for ultra-small cobalt particles formed in titania thin films via ion beam synthesis. Raw data for polarised neutron reflectometry, magnetometry and the particle size distribution are included and made available on a public repository. Additional elemental maps from scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) are also presented. Data were obtained using the following types of equipment: the NREX and PLATYPUS polarised neutron reflectometers; a Quantum Design Physical Property Measurement System (14 T); a JEOL JSM-6490LV SEM, and a JEOL ARM-200F scanning transmission electron microscope (STEM). The data is provided as supporting evidence for the article in Applied Surface Science (A. Bake et al., Appl. Surf. Sci., vol. 570, p. 151068, 2021, DOI 10.1016/j.apsusc.2021.151068), where a full discussion is given. The additional supplementary reflectometry and modelling datasets are intended to assist future scientific software development of advanced fitting algorithms for magnetization gradients in thin films.

Formation of Pt-Based Alloy Nanoparticles Assisted by Molybdenum Hexacarbonyl.

We report on an optimized, scalable solution-phase synthetic procedure for the fabrication of fine-tuned monodisperse nanostructures (Pt(NiCo), PtNi and PtCo). The influence of different solute metal precursors and surfactants on the morphological evolution of homogeneous alloy nanoparticles (NPs) has been investigated. Molybdenum hexacarbonyl (Mo(CO)6) was used as the reductant. We demonstrate that this solution-based strategy results in uniform-sized NPs, the morphology of which can be manipulated by appropriate selection of surfactants and solute metal precursors. Co-surfactants (oleylamine, OAm, and hexadecylamine, HDA) enabled the development of a variety of high-index faceted NP morphologies with varying degrees of curvatures while pure OAm selectively produced octahedral NP morphologies. This Mo(CO)6-based synthetic protocol offers new avenues for the fabrication of multi-structured alloy NPs as high-performance electrocatalysts.

Oleylamine Aging of PtNi Nanoparticles Giving Enhanced Functionality for the Oxygen Reduction Reaction.

We report a rapid solution-phase strategy to synthesize alloyed PtNi nanoparticles which demonstrate outstanding functionality for the oxygen reduction reaction (ORR). This one-pot coreduction colloidal synthesis results in a monodisperse population of single-crystal nanoparticles of rhombic dodecahedral morphology with Pt-enriched edges and compositions close to Pt1Ni2. We use nanoscale 3D compositional analysis to reveal for the first time that oleylamine (OAm)-aging of the rhombic dodecahedral Pt1Ni2 particles results in Ni leaching from surface facets, producing aged particles with concave faceting, an exceptionally high surface area, and a composition of Pt2Ni1. We show that the modified atomic nanostructures catalytically outperform the original PtNi rhombic dodecahedral particles by more than two-fold and also yield improved cycling durability. Their functionality for the ORR far exceeds commercially available Pt/C nanoparticle electrocatalysts, both in terms of mass-specific activities (up to a 25-fold increase) and intrinsic area-specific activities (up to a 27-fold increase).

Investigating the cadmium adsorption capacities of crop straw biochars produced using various feedstocks and pyrolysis temperatures.

Cadmium pollution in the environment is ubiquitous and can be a serious health issue. Crop straw-based biochar is a promising adsorbent, yet few studies have systematically examined the effects of both feedstock and pyrolysis temperature on biochar efficacy for cadmium (Cd) sorption. Sorption-desorption experiments were conducted to explore the mechanisms of Cd sorption for biochars derived from wheat straw (WSB), rape straw (RASB), soybean straw (SSB), and peanut straw (PSB) feedstocks, which were produced by pyrolysis at 450 °C and 650 °C. For biochars pyrolyzed at 450 °C, the sorption capacities varied as PSB>SSB>RASB≈WSB, while the order changed as RASB≈WSB>PSB>SSB for 650 °C biochars. With the increase in pyrolysis temperature, for wheat straw biochar and rape straw biochars, Cd sorption capacities increased by 72% and 63%, while there were 61% and 63% decreases for peanut straw biochar and soybean straw biochar, respectively. Compared to the non-legume straw biochars (WSB and RASB), legume straw biochars (SSB and PSB) have higher sorption capacities for Cd. Peanut straw biochar (PSB) produced at 450 °C was found to be the most promising adsorbent for cadmium. Examination of the sorbed biochars using a range of analytical techniques indicated that 450 °C PSB immobilized cadmium by precipitation with non-electrostatic adsorption. The precipitation of Cd on 450 °C PSB was mainly induced by cation exchange between Cd with mineral cations, which caused Cd complexation with carboxyl functional groups.

Advanced characterization of biomineralization at plaque layer and inside rice roots amended with iron- and silica-enhanced biochar.

Application of iron (Fe)- and silica (Si)-enhanced biochar compound fertilisers (BCF) stimulates rice yield by increasing plant uptake of mineral nutrients. With alterations of the nutrient status in roots, element homeostasis (e.g., Fe) in the biochar-treated rice root was related to the formation of biominerals on the plaque layer and in the cortex of roots. However, the in situ characteristics of formed biominerals at the micron and sub-micron scale remain unknown. In this study, rice seedlings (Oryza sativa L.) were grown in paddy soil treated with BCF and conventional fertilizer, respectively, for 30 days. The biochar-induced changes in nutrient accumulation in roots, and the elemental composition, distribution and speciation of the biomineral composites formed in the biochar-treated roots at the micron and sub-micron scale, were investigated by a range of techniques. Results of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that biochar treatment significantly increased concentrations of nutrients (e.g., Fe, Si, and P) inside the root. Raman mapping and vibrating sample magnetometry identified biochar particles and magnetic Fe nanoparticles associated with the roots. With Fe plaque formation, higher concentrations of FeOx- and FeOxH- anions on the root surface than the interior were detected by time-of-flight secondary ionization mass spectrometry (ToF-SIMS). Analysis of data from scanning electron microscopy energy-dispersive spectroscopy (SEM-EDS), and from scanning transmission electron microscopy (STEM) coupled with EDS or energy electron loss spectroscopy (EELS), determined that Fe(III) oxide nanoparticles were accumulated in the crystalline fraction of the plaque and were co-localized with Si and P on the root surface. Iron-rich nanoparticles (Fe-Si nanocomposites with mixed oxidation states of Fe and ferritin) in the root cortex were identified by using aberration-corrected STEM and in situ EELS analysis, confirming the biomineralization and storage of Fe in the rice root. The findings from this study highlight that the deposition of Fe-rich nanocomposites occurs with contrasting chemical speciation in the Fe plaque and cortex of the rice root. This provides an improved understanding of the element homeostasis in rice with biochar-mineral fertilization.

Graphene inclusion induced ultralow thermal conductivity and improved figure of merit in p-type SnSe.

The concept of composite material has been increasingly applied for the significant improvement in the thermoelectric performance because of the predictable effective medium properties and the unique interfacial correlated thermal and electrical transport mechanism. Herein, we report that the graphene inclusion can lead to a significant reduction in thermal conductivity and improve the overall thermoelectric figure-of-merit in SnSe. We demonstrate a systematic investigation on the microstructures and electrical and thermoelectric properties of the SnSe/graphene composite. HRTEM reveals the uniform distribution of graphene nanosheets in the SnSe matrix, forming a sharp interface with refined SnSe grain sizes and defects nearby the interfaces. Thermal conductivity decreases with graphene addition and can significantly reduce to as low as ∼0.18 W m-1 K-1, resulting in an enhanced figure of merit (ZT) of the SnSe/graphene composite by at least 50% compared with pristine SnSe. The significant reduction in thermal conductivity is attributed to the phonon scattering by densely distributed phase interfaces as well as defects and grain boundaries. The carbon element is also believed to potentially reduce long-range tin diffusion by acting as a confinement barrier to restrict heat and ion diffusion. Our work proves that the graphene secondary phase could enhance the ZT of the SnSe matrix, which might pave the way for achieving high-performance thermoelectric properties in carbon-induced composite materials.

Intrinsic Effect of Nanoparticles on the Mechanical Rupture of Doubled-Shell Colloidal Capsule via In Situ TEM Mechanical Testing and STEM Interfacial Analysis.

The discovery of Pickering emulsion templated assembly enables the design of a hybrid colloidal capsule with engineered properties. However, the underlying mechanisms by which nanoparticles affect the mechanical properties of the shell are poorly understood. Herein, in situ mechanical compression on the transmission electron microscope and aberration-corrected scanning transmission microscope are unprecedentedly implemented to study the intrinsic effect of nanoparticles on the mechanical properties of the calcium carbonate (CaCO3 )-decorated silica (SiO2 ) colloidal capsule. The stiff and brittle nature of the colloidal capsule is due to the interfacial chemical bonding between the CaCO3 nanoparticles and SiO2 inner shell. Such bonding strengthens the mechanical strength of the SiO2 shell (166 ± 14 nm) from the colloidal capsule compared to the thicker single SiO2 shell (310 ± 70 nm) from the silica hollow sphere. At elevated temperature, this interfacial bonding accelerates the formation of the single calcium silicate shell, causing shell morphology transformation and yielding significantly enhanced mechanical strength by 30.9% and ductility by 94.7%. The superior thermal durability of the heat-treated colloidal capsule holds great potential for the fabrication of the functional additives that can be applied in the wide range of applications at elevated temperatures.

Wheat straw vinegar: A more cost-effective solution than chemical fungicides for sustainable wheat plant protection.

Fusarium head blight (FHB), caused by the fungal pathogen Fusarium graminearum, is a destructive and widespread wheat disease. Chemical fungicides are becoming less effective at reducing the disease severity of FHB, and there is a need to find a more effective, low-cost natural product. A by-product of the pyrolysis of wheat straw is a condensate known as wheat straw vinegar, which was hypothesized to be an effective F. graminearum inhibitor in wheat. The organic and mineral compositions of wheat straw vinegar were analyzed. The results of GC-MS indicated that the major organic compounds in wheat straw vinegar are phenolics and acetic acid. The main inorganic elements in the liquid were K, Ca, S and Mg. A bio-test of wheat straw vinegar showed strong antifungal activity on F. graminearum growth and production of deoxynivalenol (DON) with an EC50 (concentration for 50% of maximal effect) value of 3.1 µl ml-1. Field tests showed that the application of wheat straw vinegar diluted 200-fold significantly decreased the wheat FHB infection rate and DON content by 66% and 69%, respectively. The control efficacy of wheat straw vinegar at a dilution of 200-fold was similar to that of typical chemical fungicide applications. The use of wheat straw vinegar may increase farmers' income by reducing the net fungicide costs. Therefore, wheat straw vinegar has high potential as a natural fungicide for the control of FHB and can reduce the dependence on synthetic fungicides.

Biochar increases soil organic carbon, avocado yields and economic return over 4 years of cultivation.

The use of biochar in avocado orchard soils has not yet been investigated in rigorous scientific experiments. We determine the effect of wood biochar on avocado growth, fruit production and economic benefit. Biochar was applied at 0%, 5%, 10% and 20% volume by volume basis. Biochar significantly improved the growth of avocado seedlings and increased fruit yield in the first three years after planting. There was an overall increase in soil carbon, fruit yield, tree diameter and height in all biochar treatments relative to the control over the seasons. Trees planted with biochar had 18-26% greater growth rates (in terms of height and stem diameter) than the control. Tree diameter was significantly greater with biochar (145.4 ± 3.3 mm) relative to the control treatment (125.0 ± 2.7 mm). Tree height was also significantly greater with biochar (3.7 ± 0.1 m) relative to the control treatment (3.4 ± 0.1 m). The fruit count from the biochar row was significantly greater (97%) in 2018. Heavy bearing trees typically have a lower yield in the subsequent year but despite this, the 2019 fruit counts were higher in aggregate for the biochar amended trees (20%) relative to the control. A cost-benefit analysis indicated that if yield surplus of fruit trees continued for three years, and assuming avocado prices remain at similar levels, then the discounted net benefit over a hectare would amount to US$8581, or US$105 per metric tonne of biochar applied.

Propulsive nanomachines: the convergent evolution of archaella, flagella and cilia.

Echoing the repeated convergent evolution of flight and vision in large eukaryotes, propulsive swimming motility has evolved independently in microbes in each of the three domains of life. Filamentous appendages - archaella in Archaea, flagella in Bacteria and cilia in Eukaryotes - wave, whip or rotate to propel microbes, overcoming diffusion and enabling colonization of new environments. The implementations of the three propulsive nanomachines are distinct, however: archaella and flagella rotate, while cilia beat or wave; flagella and cilia assemble at their tips, while archaella assemble at their base; archaella and cilia use ATP for motility, while flagella use ion-motive force. These underlying differences reflect the tinkering required to evolve a molecular machine, in which pre-existing machines in the appropriate contexts were iteratively co-opted for new functions and whose origins are reflected in their resultant mechanisms. Contemporary homologies suggest that archaella evolved from a non-rotary pilus, flagella from a non-rotary appendage or secretion system, and cilia from a passive sensory structure. Here, we review the structure, assembly, mechanism and homologies of the three distinct solutions as a foundation to better understand how propulsive nanomachines evolved three times independently and to highlight principles of molecular evolution.

Enhancing the Thermoelectric Performance of Polycrystalline SnSe by Decoupling Electrical and Thermal Transport through Carbon Fiber Incorporation.

Thermoelectric (TE) materials have attracted extensive interest because of their ability to achieve direct heat-to-electricity conversion. They provide an appealing renewable energy source in a variety of applications by harvesting waste heat. The record-breaking figure of merit reported for single crystal SnSe has stimulated related research on its polycrystalline counterpart. Boosting the TE conversion efficiency requires increases in the power factor and decreases in thermal conductivity. It is still a big challenge, however, to optimize these parameters independently because of their complex interrelationships. Herein, we propose an innovative approach to decouple electrical and thermal transport by incorporating carbon fiber (CF) into polycrystalline SnSe. We show that the incorporation of highly conductive CF can successfully enhance the electrical conductivity, while greatly reducing the thermal conductivity of polycrystalline SnSe. As a result, a high TE figure-of-merit (zT) of 1.3 at 823 K is obtained in p-type SnSe/CF composite polycrystalline materials. Furthermore, SnSe samples incorporated with CFs exhibit superior mechanical properties, which are favorable for device fabrication applications. Our results indicate that the dispersion of CF can be a good way to greatly improve both TE and mechanical performance.

Biochar-based fertilizer: Supercharging root membrane potential and biomass yield of rice.

Biochar-based compound fertilizers (BCF) and amendments have proven to enhance crop yields and modify soil properties (pH, nutrients, organic matter, structure etc.) and are now in commercial production in China. While there is a good understanding of the changes in soil properties following biochar addition, the interactions within the rhizosphere remain largely unstudied, with benefits to yield observed beyond the changes in soil properties alone. We investigated the rhizosphere interactions following the addition of an activated wheat straw BCF at an application rates of 0.25% (g·g-1 soil), which could potentially explain the increase of plant biomass (by 67%), herbage N (by 40%) and P (by 46%) uptake in the rice plants grown in the BCF-treated soil, compared to the rice plants grown in the soil with conventional fertilizer alone. Examination of the roots revealed that micron and submicron-sized biochar were embedded in the plaque layer. BCF increased soil Eh by 85 mV and increased the potential difference between the rhizosphere soil and the root membrane by 65 mV. This increased potential difference lowered the free energy required for root nutrient accumulation, potentially explaining greater plant nutrient content and biomass. We also demonstrate an increased abundance of plant-growth promoting bacteria and fungi in the rhizosphere. We suggest that the redox properties of the biochar cause major changes in electron status of rhizosphere soils that drive the observed agronomic benefits.

Topographical and compositional engineering of core-shell Ni@Pt ORR electro-catalysts.

Complex faceted geometries and compositional anisotropy in alloy nanoparticles (NPs) can enhance catalytic performance. We report on the preparation of binary PtNi NPs via a co-thermolytic approach in which we optimize the synthesis variables, which results in significantly improved catalytic performance. We used scanning transmission electron microscopy to characterise the range of morphologies produced, which included spherical and concave cuboidal core-shell structures. Electrocatalytic activity was evaluated using a rotating disc electrode (1600 rpm) in 0.1 M HClO4; the electrocatalytic performance of these Ni@Pt NPs showed significant (∼11-fold) improvement compared to a commercial Pt/C catalyst. Extended cycling revealed that electrochemical surface area was retained by cuboidal PtNi NPs post 5000 electrochemical cycles (0.05-1.00 V, vs. SHE). This is attributed to the enclosure of Ni atoms by a thick Pt shell, thus limiting Ni dissolution from the alloy structures. The novel synthetic strategy presented here results in a high yield of Ni@Pt NPs which show excellent electro-catalytic activity and useful durability.