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Abstract We report the first instance of deposition of preferentially oriented, nanocrystalline, and nanocolumnar strontium-doped lead zirconate titanate (PSZT) ferroelectric thin films directly on thermal silicon dioxide. No intermediate seed or activation layers were used between PSZT and silicon dioxide. The deposited thin films have been characterised using a combination of diffraction and microscopy techniques.

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 × 10 16 at cm -2 yields a surface η-Mo 3 C 2 with a particle diameter of (10 ± 1) nm. Molybdenum implantation into glassy carbon at 60 keV to a fluence of 6 × 10 16 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 β-Mo 2 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., (© 2023 Wiley‐VCH GmbH.)

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., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

The current study investigates the therapeutic and optical properties of bismuth oxide (Bi 2 O 3 ) particles for selective melanoma therapy and prevention. The Bi 2 O 3 particles were prepared using a standard precipitation method. The Bi 2 O 3 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 Bi 2 O 3 a theranostic material. Moreover, Bi 2 O 3 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 Bi 2 O 3 particles surrounding the treatment and prevention of melanoma., (© 2023 The Authors. Journal of Biomedical Materials Research Part A published by Wiley Periodicals LLC.)

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 H 2 O 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.

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 CaCO 3 ) 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 HCO 3 - ; 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.

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., (© 2022 The Author. Microscopy Research and Technique published by Wiley Periodicals LLC.)

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 15 N-NH 4 + 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 15 N 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

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., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships which have or could be perceived to have influenced the work reported in this article., (Crown Copyright © 2021 Published by Elsevier Inc.)

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.

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 Pt 1 Ni 2 . We use nanoscale 3D compositional analysis to reveal for the first time that oleylamine (OAm)-aging of the rhombic dodecahedral Pt 1 Ni 2 particles results in Ni leaching from surface facets, producing aged particles with concave faceting, an exceptionally high surface area, and a composition of Pt 2 Ni 1 . 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).

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.

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 FeO x - and FeO x H - 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.

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 HClO 4 ; 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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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 EC 50 (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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 (CaCO 3 )-decorated silica (SiO 2 ) colloidal capsule. The stiff and brittle nature of the colloidal capsule is due to the interfacial chemical bonding between the CaCO 3 nanoparticles and SiO 2 inner shell. Such bonding strengthens the mechanical strength of the SiO 2 shell (166 ± 14 nm) from the colloidal capsule compared to the thicker single SiO 2 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., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

The potential of biochar to enhance phytorestoration of hexavalent chromium [Cr(VI)]-contaminated soils was investigated. Rooted cuttings of Ficus elastica Roxb. Ex Hornem were transplanted to soil treated with 0 or 25 mg kg -1 Cr(VI), ‒Cr and +Cr designations respectively, and amended with cattle manure-derived biochar at 0, 10 and 50 g kg -1 . Plants were grown for 180 d in a temperature-controlled greenhouse. In the ‒Cr treatment, biochar addition enhanced plant growth without affecting plant water status, leaf nutrient levels, photochemical efficiency, or hormone levels. In the absence of biochar, Ficus growth in the +Cr treatment was stunted, exhibiting decreased leaf and root relative water content and photochemical efficiency. Adding biochar to +Cr soil resulted in decreased Cr uptake into plant tissues and alleviated the toxic effects of soil Cr(VI) on plant growth and physiology, including decreased leaf lipid peroxidation. High-resolution electron microscopy and spectroscopy elucidated the biochar role in decreasing Cr mobility, bioavailability, and phytotoxicity. Spectroscopic evidence is suggestive that biochar mediated the reduction of Cr(VI) to Cr(III), which was subsequently incorporated into organomineral agglomerates formed at biochar surfaces. The dual function of biochar in improving F. elastica performance and detoxifying Cr(VI) demonstrates that biochar holds much potential for enhancing phytorestoration of Cr(VI)-contaminated soils., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Over use of N fertilizers, most commonly as urea, had been seriously concerned as a major source of radiative N (Nr) for severe environment impacts through leaching, volatilization, and N 2 O emission from fertilized croplands. It had been well known that biochar could enhance N retention and use efficiency by crops in amended croplands. In this study, a granular biochar-mineral urea composite (Bio-MUC) was obtained by blending urea with green waste biochar supplemented with clay minerals of bentonite and sepiolite. This Bio-MUC material was firstly characterized by microscopic analyses with FTIR, SEM-EDS and STEM, subsequently tested for N leaching in water in column experiment and for N supply for maize in pot culture, compared to conventional urea fertilizer (UF). Microscopic analyses indicated binding of urea N to particle surfaces of biochar and clay minerals in the Bio-MUC composite. In the leaching experiment over 30 days, cumulative N release as NH 4 + -N and of dissolved organic carbon (DOC) was significantly smaller by >70% and by 8% from the Bio-MUC than from UF. In pot culture with maize growing for 50 days, total fresh shoot was enhanced by 14% but fresh root by 25% under Bio-MUC compared to UF. This study suggested that N in the Bio-MUC was shown slow releasing in water but maize growth promoting in soil, relative to conventional urea. Such effect could be related mainly to N retention by binding to biochar/mineral surfaces and partly by carbon bonds of urea to biochar in the Bio-MUC. Therefore, biochar from agro-wastes could be used for blending urea as combined organo/mineral urea to replace mineral urea so as to reduce N use and impacts on global Nr. Of course, how such biochar combined urea would impact N process in soil-plant systems deserve further field studies., (Copyright © 2019 The Author(s). Published by Elsevier B.V. All rights reserved.)

Biowaste eggshell can be used as a cathode while in its calcined form and it is found to be suitable as an anode in an electrochemical cell. This not only enables energy to be stored reversibly but also achieves waste management and sustainability goals by redirecting material away from landfill. Biowaste eggshell comprises 94% calcium carbonate (CaCO 3 ; calcite), an attractive divalent ion source as a viable option for energy storage. X-ray diffraction and electron microscopy coupled with energy dispersive analyses of the calcined (thermally decomposed) biowaste eggshell show that CaO has been formed and the reaction is topotactic. Field emission scanning electron microscopy (FESEM) images of the textural relationship show that the thermal decomposition of calcite resulted in a change in morphology. High-resolution XPS spectra of the C 1s core level from the CaCO 3 and CaO shows that there is a chemical difference in the carbon environments and the total atomic fraction of Ca for each sample with that of carbonate and oxygen varies. In a three-electrode configuration, a working electrode of CaCO 3 is found to be electrochemically active in the positive region, whereas a CaO electrode is active in the negative region. This indicates the potential use of eggshell-derived materials for both cathode and anode. Both the electrodes exhibited a quasi-box-shaped potentiostatic curve implying a capacitor-type behaviour. The CaCO 3 cathode possesses a modest discharge capacitance of 10 F g -1 but the CaO anode showed excellent capacitance value of 47.5 F g -1 . The CaO electrode in both positive and negative regions, at a current density of 0.15 A g -1 exhibited 55 F g -1 with a retention of nearly 100% after 1000 cycles. At a very low sweep rate of 0.5 mV s -1 , the CaO electrode showed typical redox-type behaviour with well-defined peaks illustrating battery-type behaviour. The outcome of the calcite/CaO transformation, exhibiting technological importance for energy storage applications, may help to re-evaluate biowaste before throwing it away. The current work explores the viability of eggshell derived materials as a cathode/anode for use in batteries and capacitors., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Bio-waste in the form of chicken eggshells, which contain high amounts of calcium carbonate (CaCO3), is used to store energy. The fine eggshell powders are used as an electrode against a metallic lithium anode in a non-aqueous electrolyte. The initial discharge capacitance of the eggshell system was found to be 232 F g-1, while the reversible capacitance was 120 F g-1. Thereon, the cell maintained an excellent capacitance retention of 92% over 1000 cycles. The electrochemical performance obtained is comparable to that of commercially available classical activated carbon (AC) material. CaCO3 showed a non-faradaic behaviour and the shape of the electrochemical curves resembles that of the AC electrode. The preliminary findings suggest that CaCO3 from eggshells can be used as the electrode in Li-ion capacitors to store and release charges effectively over a wide electrochemical stability window of 4 V. Using chicken eggshells in this manner not only reduces the amount of bio-waste, but also adds considerable value. A detailed understanding of the electrochemical and physical behaviour of the material is needed in order to improve its performance and to enable its widespread use.

Silicon-based impurities are ubiquitous in natural graphite. However, their role as a contaminant in exfoliated graphene and their influence on devices have been overlooked. Herein atomic resolution microscopy is used to highlight the existence of silicon-based contamination on various solution-processed graphene. We found these impurities are extremely persistent and thus utilising high purity graphite as a precursor is the only route to produce silicon-free graphene. These impurities are found to hamper the effective utilisation of graphene in whereby surface area is of paramount importance. When non-contaminated graphene is used to fabricate supercapacitor microelectrodes, a capacitance value closest to the predicted theoretical capacitance for graphene is obtained. We also demonstrate a versatile humidity sensor made from pure graphene oxide which achieves the highest sensitivity and the lowest limit of detection ever reported. Our findings constitute a vital milestone to achieve commercially viable and high performance graphene-based devices.

The design of a suitable electrode is an essential and fundamental research challenge in the field of electrochemical energy storage because the electronic structures and morphologies determine the surface redox reactions. Calcium molybdate (CaMoO 4 ) was synthesized by a combustion route at 300 °C and 500 °C. We describe new findings on the behaviour of CaMoO 4 and evaluate the influence of crystallinity on energy storage performance. A wide range of characterization techniques was used to obtain detailed information about the physical and morphological characteristics of CaMoO 4 . The characterization results enable the phase evolution as a function of the electrode synthesis temperature to be understood. The crystallinity of the materials was found to increase with increasing temperature but with no second phases observed. Molecular dynamics simulation of electronic structures correlated well with the experimental findings. These results show that to enable faster energy storage and release for a given surface area, amorphous CaMoO 4 is required, while larger energy storage can be obtained by using crystalline CaMoO 4 . CaMoO 4 has been evaluated as a cathode material in classical lithium-ion batteries recently. However, determining the surface properties in a sodium-ion system experimentally, combined with computational modelling to understand the results has not been reported. The superior electrochemical properties of crystalline CaMoO 4 are attributed to its morphology providing enhanced Na + ion diffusivity and electron transport. However, the presence of carbon in amorphous CaMoO 4 resulted in excellent rate capability, suitable for supercapacitor applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Magnesium molybdate (MgMoO4), which possesses synergistic features combining both hierarchical plate-like nanomaterials and porous architectures, has been successfully synthesized through a facile combustion synthesis at a low temperature. The hierarchical architecture is characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), scanning transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analyses. The as-obtained MgMoO4 nanoplates showed a porous structure with a pore-size distribution ranging from 50 to 70 nm. This porosity provides an electron transport pathway and enhanced surface reaction kinetics. The binding energies measured for Mg 2p, Mo 3d, 3p and O 1s are consistent with the literature, and with the metal ions being present as M(ii) and M(vi) states, respectively. This indicates that the oxidation states of the metal cations are as expected. The electrochemical behaviour of MgMoO4 was investigated using aqueous (NaOH) and non-aqueous solvents (NaClO4 in EC : DMC : FEC) for supercapacitor and battery applications. The sodium-ion capacitor involves ion absorption and insertion into the MgMoO4 electrodes resulting in superior power and energy densities. However, the cycling stability was found to be stable only for an aqueous system. The formation of a solid electrolyte surface layer restricted the reversible capacity of the MgMoO4 in the sodium-battery. Nevertheless, it does offer some promise as an anode material for storing energy with high rate performance and excellent capacity retention. Detailed comparative analyses of various electrolytes in storage devices such as hybrid sodium-ion capacitors and sodium-ion batteries are vital for the integration of hierarchical structured materials into practical applications. The reaction mechanisms are postulated.

Nanoalloys with anisotropic morphologies of branched and porous internal structures show great promise in many applications as high performance materials. Reported synthetic approaches for branched alloy nanostructures are, however, limited by the synthesis using a seed-growth process. Here, we demonstrate a conveniently fast and one-pot solution-phase thermal reduction strategy yielding nanoalloys of Pt with various solute feed ratios, exhibiting hyperbranched morphologies and good dispersity. When Pt was alloyed with transition metals (Ni, Co, Fe), we observed well-defined dendritic nanostructures in PtNi, PtCo and Pt(NiCo), but not in PtFe, Pt(FeNi) or Pt(FeCo) due to the steric hindrance of the trivalent Fe(acac)₃ precursor used during synthesis. In the case of Pt-based nanoalloys containing Ni and Co, the dendritic morphological evolution observed was insensitive to large variations in solute concentration. The functionality of these nanoalloys towards the oxygen reduction reaction (ORR); however, was observed to be dependent on the composition, increasing with increasing solute content. Pt₃(NiCo)₂ exhibited superior catalytic activity, affording about a five- and 10-fold enhancement in area-specific and mass-specific catalytic activities, respectively, compared to the standard Pt/C nanocatalyst. This solution-based synthetic route offers a new approach for constructing dendritic Pt-based nanostructures with excellent product yield, monodispersity and high crystallinity.

Recent studies have demonstrated the importance of the nutrient status of biochar and soils prior to its inclusion in particular agricultural systems. Pre-treatment of nutrient-reactive biochar, where nutrients are loaded into pores and onto surfaces, gives improved yield outcomes compared to untreated biochar. In this study we have used a wide selection of spectroscopic and microscopic techniques to investigate the mechanisms of nutrient retention in a high temperature wood biochar, which had negative effects on Chenopodium quinoa above ground biomass yield when applied to the system without prior nutrient loading, but positive effects when applied after composting. We have compared non-composted biochar (BC) with composted biochar (BCC) to elucidate the differences which may have led to these results. The results of our investigation provide evidence for a complex series of reactions during composting, where dissolved nutrients are first taken up into biochar pores along a concentration gradient and through capillary action, followed by surface sorption and retention processes which block biochar pores and result in deposition of a nutrient-rich organomineral (plaque) layer. The lack of such pretreatment in the BC samples would render it reactive towards nutrients in a soil-fertilizer system, making it a competitor for, rather than provider of, nutrients for plant growth., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Recent studies have shown that the pyrolysis of biomass combined with clay can result in both lower cost and increase in plant yields. One of the major sources of nutrients for pasture growth, as well as fuel and building materials in Tibet is yak dung. This paper reports on the initial field testing in a pasture setting in Tibet using yak dung, biochar, and attapulgite clay/yak dung biochars produced at ratios of 10/90 and 50/50 clay to dung. We found that the treatment with attapulgite clay/yak dung (50/50) biochar resulted in the highest pasture yields and grass nutrition quality. We also measured the properties and yields of mixtures of clay/yak dung biochar used in the field trials produced at 400°C and 500°C to help determine a possible optimum final pyrolysis temperature and dung/clay ratio. It was observed that increasing clay content increased carbon stability, overall biochar yield, pore size, carboxyl and ketone/aldehyde functional groups, hematite and ferrous/ferric sulphate/thiosulphate concentration, surface area and magnetic moment. Decreasing clay content resulted in higher pH, CEC, N content and an enhanced ability to accept and donate electrons. The resulting properties were a complex function of both processing temperature and the percentage of clay for the biochars processed at both 400°C and 500°C. It is possible that the increase in yield and nutrient uptake in the field trial is related to the higher concentration of C/O functional groups, higher surface area and pore volume and higher content of Fe/O/S nanoparticles of multiple oxidation state in the 50/50 clay/dung. These properties have been found to significantly increase the abundance of beneficial microorganisms and hence improve the nutrient cycling and availability in soil. Further field trials are required to determine the optimum pyrolysis production conditions and application rate on the abundance of beneficial microorganisms, yields and nutrient quality., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The influence of the precursors on the dispersion of Ni 2+ ions and the presence of several other functional groups was investigated in the preparation of sodium nickel phosphate (NaNiPO 4 ) cathode for a supercapacitor study. The dispersion of nickel phases, in the form of nanosheets, is influenced by the type of precursors used in the synthesis. XPS based spectroscopic information on the surface functional groups on NaNiPO 4 show differences between the precursors (i.e.) acetate- and nitrate-derived materials. The benefits of using acetate as an alternative to nitrate are explored by using the NaNiPO 4 nanoparticles as a cathode for supercapacitor applications. The acetate-derived material exhibits improved electrochemical properties possessing both redox behaviour and double-layer capacitance. The results indicate that the metal acetates are homogenously distributed. Acetate functionalization resulted in an improved capacitance of 90 F g -1 compared with that obtained from the nitrate precursor derived material (58 F g -1 ). Capacitance retention and high rate capability were also a feature of the acetate-derived material. The sodium nickel phosphate cathode material has provided useful insights on the precursor chemistry in storing renewable energy have been reported for the first time.

Understanding how an adaptive integrated interface between lubricant additives and solid contacts works will enable improving the wear and friction of moving engine components. This work represents the comprehensive characterization of compositional and structural orientation at the sliding interface from the perspective of surface/interface tribochemistry. The integrated interface of a lubricant additive-solid resulting from the friction testing of Graphite-like carbon (GLC) and PVD-CrN coated rings sliding against cast iron under boundary lubrication was studied. The results indicate that in the case of the CrN/cast iron pair the antiwear and friction behavior were very strongly dependent upon lubricant. In contrast, the tribology of the GLC surface showed a much lower dependence on lubrication. In order to identify the compounds and their distribution across the interface, x-ray microanalysis phase mapping was innovatively applied and the principle of hard and soft acids and bases (HSAB) to understand the behaviour. Phase mapping clearly showed the hierarchical interface of the zinc-iron polyphosphate tribofilm for various sliding pairs and different sliding durations. This interface structure formed between lubricant additives and the sliding surfaces adapts to the sliding conditions - the term adaptive interface. The current results help explain the tribology of these sliding components in engine.

Biochar and mineral-enriched biochar (MEB) have been used as soil amendments to improve soil fertility, sequester carbon and mitigate greenhouse gas emissions. Such beneficial outcomes could be partially mediated by soil bacteria, however little is known about how they directly interact with biochar or MEB. We therefore analyzed the diversity and functions of bacterial communities on the surfaces of one biochar and two different MEBs after a 140-day incubation in soil. The results show that the biochar and the MEBs harbor distinct bacterial communities to the bulk soil. Communities on biochar and MEBs were dominated by a novel Gammaproteobacterium. Genome reconstruction combined with electron microscopy and high-resolution elemental analysis revealed that the bacterium generates energy from the oxidation of iron that is present on the surface. Two other bacteria belonging to the genus Thiobacillus and a novel group within the Oxalbacteraceae were enriched only on the MEBs and they had the genetic capacity for thiosulfate oxidation. All three surface-enriched bacteria also had the capacity to fix carbon dioxide, either in a potentially strictly autotrophic or mixotrophic manner. Our results show the dominance of chemolithotrophic processes on the surface of biochar and MEB that can contribute to carbon sequestration in soil.

A software method has been developed which uses ellipse fitting to analyse electron diffraction patterns from polycrystalline materials. The method, which requires minimal user input, can determine the pattern centre and the diameter of diffraction rings with sub-pixel precision. This enables accurate crystallographic information to be obtained in a rapid and consistent manner. Since the method fits ellipses, it can detect, quantify and correct any elliptical distortion introduced by the imaging system. Distortion information derived from polycrystalline patterns as a function of camera length can be subsequently recalled and applied to single crystal patterns, resulting in improved precision and accuracy. The method has been implemented as a plugin for the DigitalMicrograph software by Gatan, and is a freely available via the internet., (Copyright © 2015 Elsevier B.V. All rights reserved.)