Biosynthesized metallic nanoparticles as fertilizers:An emerging precision agriculture strategy

Nanofertilizers increase efficiency and sustainability of agricultural crop production.Due to their nanosize properties,they have been shown to increase productivity through target delivery or slow release of nutrients,thereby limiting the rate of fertilizer application required.Nanofertilizers can be synthesized via different approaches ranging from physical and chemical to green(biological)synthesis.The green approach is preferable because it makes use of less chemicals,thereby producing less chemical contamination and it is safer in comparison to physicochemical approaches.Hence,discussion on the use of green synthesized nanoparticles as nanofertilizers is pertinent for a sustainable approach in agriculture.This review discusses recent developments and applications of biologically synthesized metallic nanoparticles that can also be used as nanofertilizers,as well as their uptake mechanisms for plant growth.Toxicity concerns of nanoparticle applications in agriculture are also discussed.

Monodisperse magnetic metallic nanoparticles: synthesis,performance enhancement, and advanced applications

Monodisperse Fe-based and Co-based nanopar-ticles exhibit unique magnetic properties. They play important roles in magnetic storage and biomedical application. Their chemical synthesis and performance enhancement draw a lot of study interest. Investigations of magnetic metallic nano-particles are very active in many scientific fields. This paper reviews the present advances in chemical synthesis, perfor-mance enhancement, and potential applications of monodis-perse Fe-based and Co-based nanoparticles.

Higher Order Multipole Potentials and Electrostatic Screening Effects on Cohesive Energy and Bulk Modulus of Metallic Nanoparticles

Higher order rnultipole potentials and electrostatic screening effects are introduced to incorporate the dan gling bonds on the surface of a metallic nanopaticle and to modify the coulornb like potential energy terms, respectively. The total interaction energy function for any rnetallic nanoparticle is represented in terms of two- and three-body potentials. The two-body part is described by dipole-dipole interaction potential, and in the three-body part, triple-dipole （DDD） and dipole-dipole-quadrupole （DDQ） terrns are included. The size-dependent cohesive energy and bulk modulus are observed to decrease with decreasing sizes, a result which is in good agreement with the experimental values of Mo and W nanoparticles.

Steam disinfection enhances bioaccessibility of metallic nanoparticles in nano-enabled silicone-rubber baby bottle teats,pacifiers,and teethers

Nano-enabled silicone-rubber articles for feeding or chewing could be a source of metallic nanoparticles(NPs)directly exposed to infants and young children.However,the impact of steam disinfection on release of NPs and the related potential risks to children's health are unknown.Here,we investigated contents and form of Ag and Zn in 57 nano-enabled silicone-rubber baby bottle teats,pacifiers,and teethers of seven countries and examined the impacts of steam disinfection on in vitro bioaccessibility(IVBA)of Ag and Zn in the articles.Nearly 89%articles had a mixture of Ag-and Zn-containing NPs and the teethers had relatively high Ag and Zn contents(up to 501 and 254μg/g,respectively).Steam disinfection caused rubber decomposition into micro(nano)plastics(0.54-15.7μm)and NP release from the interior of bulk rubber and micro-sized plastics,thus enhancing the IVBA of Ag and Zn by up to 5.5 times.The findings provide insights into mechanisms for NP release by steam disinfection.Though oral exposure risk assessment suggested low health concerns on individual metal release,our study points out the need to assess the potential health risks of child co-exposure to metallic NPs and micro(nano)plastics.

Green synthesis of functional metallic nanoparticles by dissimilatory metal-reducing bacteria“Shewanella”:A comprehensive review

The biosynthesis strategy of nanoparticles has attracted much attention due to the mild synthesis condi-tions,environmental-friendly properties,and low costs.Biosynthesized nanoparticles(bio-NPs)not only show excellent physicochemical properties,but also exhibit high stability,enlarged specific surface area,and excellent biocompatibility,which are crucial for industrial,agricultural,and medical fields.She-wanella,a kind of dissimilatory metal-reducing bacteria,is regarded as a typical biosynthesis-functional bacteria class with wide distribution and strong adaptability.Thus,in this paper,functional bio-NPs by Shewanella were reviewed to provide a comprehensive view of current research progress.The biosynthetic mechanisms of Shewanella are summarized as the Mtr pathway(predominant),extracellular polymeric substance-induced pathway,and enzyme/protein-induced pathway.During the biosynthesis process,bio-logical factors along with the physicochemical parameters highly influenced the properties of the resul-tant bio-NPs.Till now,bio-NPs have been applied in various fields including environmental remediation,antibacterial applications,and microbial fuel cells.However,some challenging issues of bio-NPs by She-wanella remain unsolved,such as optimizing suitable bacterial strains,intelligently controlling bio-NPs,clarifying biosynthesis mechanisms,and expanding bio-NPs applications.

Well-defined high entropy-metal nanoparticles:Detection of the multi-element particles by deep learning

Characterizing and control the chemical compositions of multi-element particles as single metal nanoparticles(mNPs) on the surfaces of catalytic metal oxide supports is challenging.This can be attributed to the heterogeneity and large size at the nanoscale,the poorly defined catalyst nanostructure,and thermodynamic immiscibility of the strongly repelling metallic elements.To address these challenges,an ultrasonic-assisted coincident electro-oxidation-reduction-precipitation(U-SEO-P) is presented to fabricate ultra-stable PtRuAgCoCuP NPs,which produces numerous active intermediates and induces strong metal-support interactions.To sort the active high-entropy mNPs,individual NPs are described on the support surface and the role of deep learning in understanding/predicting the features of PtRuAgCoCu@TiO_(x) catalysts is explained.Notably,this deep learning approach required minimal to no human input.The as-prepared PtRuAgCoCu@TiO_(x) catalysts can be used to catalyze various important chemical reactions,such as a high reduction conversion(100% in 30 s),with no loss of catalytic activity even after 20 cycles of nitroarene and ketone/aldehyde,which is several times higher than commercial Pt@TiO_(x) owing to individual PtRuAgCoCuP NPs on TiO_(x) surface.In this study,we present the "Totally Defined Catalysis" concept,which has enormous potential for the advancement of high-activity catalysts in the reduction of organic compounds.

Anisotropic gold nanoparticles: Preparation and applications in catalysis

Despite the high amount of scientific work dedicated to the gold nanoparticles in catalysis, most of the research has been performed utilising supported nanoparticles obtained by traditional impreg‐nation of gold salts onto a support, co‐precipitation or deposition‐precipitation methods which do not benefit from the recent advances in nanotechnologies. Only more recently, gold catalyst scien‐tists have been exploiting the potential of preforming the metal nanoparticles in a colloidal suspen‐sion before immobilisation with great results in terms of catalytic activity and the morphology con‐trol of mono‐and bimetallic catalysts. On the other hand, the last decade has seen the emergence of more advanced control in gold metal nanoparticle synthesis, resulting in a variety of anisotropic gold nanoparticles with easily accessible new morphologies that offer control over the coordination of surface atoms and the optical properties of the nanoparticles （tunable plasmon band） with im‐mense relevance for catalysis. Such morphologies include nanorods, nanostars, nanoflowers, den‐dritic nanostructures or polyhedral nanoparticles to mention a few. In addition to highlighting newly developed methods and properties of anisotropic gold nanoparticles, in this review we ex‐amine the emerging literature that clearly indicates the often superior catalytic performance and amazing potential of these nanoparticles to transform the field of heterogeneous catalysis by gold by offering potentially higher catalytic performance, control over exposed active sites, robustness and tunability for thermal‐, electro‐and photocatalysis.

Tailoring the Meso-Structure of Gold Nanoparticles in Keratin-Based Activated Carbon Toward High-Performance Flexible Sensor

Flexible biosensors with high accuracy and reliable operation in detecting pH and uric acid levels in body fluids are fabricated using well-engineered metaldoped porous carbon as electrode material.The gold nanoparticles@N-doped carbon in situ are prepared using wool keratin as both a novel carbon precursor and a stabilizer.The conducting electrode material is fabricated at 500℃ under customized parameters,which mimics A-B type(two different repeating units) polymeric material and displays excellent deprotonation performance(pH sensitivity).The obtained pH sensor exhibits high pH sensitivity of 57 mV/pH unit and insignificant relative standard deviation of 0.088%.Conversely,the composite carbon material with sp^2 structure prepared at 700℃ is doped with nitrogen and gold nanoparticles,which exhibits good conductivity and electrocatalytic activity for uric acid oxidation.The uric acid sensor has linear response over a range of 1-150 μM and a limit of detection 0.1 μM.These results will provide new avenues where biological material will be the best start,which can be useful to target contradictory applications through molecular engineering at mesoscale.

ZnO,TiO_2,SiO_2,and Al_2O_3 Nanoparticles-induced Toxic Effects on Human Fetal Lung Fibroblasts

Objective This study aims to investigate and compare the toxic effects of four types of metal oxide （ZnO, TiO2, SiO2, and Al2O3） nanoparticles with similar primary size （-20 nm） on human fetal lung fibroblasts （HFL1） in vitro.Methods The HFL1 cells were exposed to the nanoparticles, and toxic effects were analyzed by using MTT assay, cellular morphology observation and Hoechst 33 258 staining.Results The results show that the four types of metal oxide nanoparticles lead to cellular mitochondrial dysfunction, morphological modifications and apoptosis at the concentration range of 0.25-1.50 mg/mL and the toxic effects are obviously displayed in dose-dependent manner. ZnO is the most toxic nanomaterials followed by TiO2, SiO2, and Al2O3 nanoparticles in a descending order.Conclusion The results highlight the differential cytotoxicity associated with exposure to ZnO, TiO2, SiO2, and Al2O3 nanoparticles, and suggest an extreme attention to safety utilization of these nanomaterials.

State of arts on the bio-synthesis of noble metal nanoparticles and their biological application

Nanomaterials are materials in which at least one of the dimensions of the particles is 100 nm and below.There are many types of nanomaterials,but noble metal nanoparticles are of interest due to their uniquely large surface-to-volume ratio,high surface area,optical and electronic properties,high stability,easy synthesis,and tunable surface functionalization.More importantly,noble metal nanoparticles are known to have excellent compatibility with bio-materials,which is why they are widely used in biological applications.The synthesis method of noble metal nanoparticles conventionally involves the reduction of the noble metal salt precursor by toxic reaction agents such as NaBH4,hydrazine,and formaldehyde.This is a major drawback for researchers involved in biological application researches.Hence,the bio-synthesis of noble metal nanoparticles(NPs)by bio-materials via bio-reduction provides an alternative method to synthesize noble metal nanoparticles which are potentially non-toxic and safer for biological application.In this review,the bio-synthesis of noble metal nanoparticle including gold nanoparticle(AuNPs),silver nanoparticle(AgNPs),platinum nanoparticle(PtNPs),and palladium nanoparticle(PdNPs)are first discussed.This is followed by a discussion of these biosynthesized noble metal in biological applications including antimicrobial,wound healing,anticancer drug,and bioimaging.Based on these,it can be concluded that the study on bio-synthesized noble metal nanoparticles will expand further involving bio-reduction by unexplored bio-materials.However,many questions remain on the feasibility of bio-synthesized noble metal nanoparticles to replace existing methods on various biological applications.Nevertheless,the current development of the biological application by bio-synthesized noble metal NPs is still intensively ongoing,and will eventually reach the goal of full commercialization.

Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid

Encapsulating noble metal nanoparticles(NPs)within the zeolite framework enhances the stability and accessibility of active sites;however,direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions.Herein,beta zeolite-encapsulated Pt NPs(Pt@Beta)were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step.The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species.Thus,the resultant 0.2%Pt@Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid(FDCA)under atmospheric O2 conditions by using water as the solvent while stably evincing a high yield(90%)associated with a large turnover number of 176.The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.

Hybrid sub-gridding ADE–FDTD method of modeling periodic metallic nanoparticle arrays

In this paper, a modified sub-gridding scheme that hybridizes the conventional finite-difference time-domain（FDTD）method and the unconditionally stable locally one-dimensional（LOD） FDTD is developed for analyzing the periodic metallic nanoparticle arrays. The dispersion of the metal, caused by the evanescent wave propagating along the metal-dielectric interface, is expressed by the Drude model and solved with a generalized auxiliary differential equation（ADE） technique.In the sub-gridding scheme, the ADE–FDTD is applied to the global coarse grids while the ADE–LOD–FDTD is applied to the local fine grids. The time step sizes in the fine-grid region and coarse-grid region can be synchronized, and thus obviating the temporal interpolation of the fields in the time-marching process. Numerical examples about extraordinary optical transmission through the periodic metallic nanoparticle array are provided to show the accuracy and efficiency of the proposed method.

One-pot synthesis and optical properties of In- and Sn-doped ZnO nanoparticles

Colloidal indium-doped zinc oxide (IZO) and tin-doped zinc oxide (ZTO) nanoparticles were successfully prepared in organic solution, with metal acetylacetonate as the precursor and oleylamine as the solvent. The crystal and optical properties were characterized by X-ray diffraction, UV−visible spectrophotometry, and fluorescence spectroscopy, respectively; the surface and structure morphologies were observed by scanning electron microscopy and transmission electron microscopy. The XRD patterns of the IZO and ZTO nanoparticles all exhibited similar diffraction peaks consistent with the standard XRD pattern of ZnO, although the diffraction peaks of the IZO and ZTO nanoparticles were slightly shifted with increasing dopant concentration. With increasing dopant concentration, the fluorescent emission peaks of the IZO nanoparticles exhibited an obvious red shift because of the difference in atomic radii of indium and zinc, whereas those of the ZTO nanoparticles exhibited almost no shift because of the similarity in atomic radii of tin and zinc. Furthermore, the sizes of the IZO and ZTO nanoparticles distributed in the ranges 20–40 and 20–25 nm, respectively, which is attributed to the difference in ionic radii of indium and tin. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

STUDY ON THE INTERACTION BETWEEN POLYVINYLPYRROLIDONE AND PLATINUM METALS DURING THE FORMATION OF THE COLLOIDAL METAL NANOPARTICLES

Several PVP-stabilized colloidal platinum metals nanoparticles have been synthesized and characterized by FTIR and TEM.Comparing with the pure PVP,carbonyl groups of PVP in the mixture of PVP and the metal precursors or in the PVP-stabilized metal nanoparticles have obvious peak shifts in FTIR spectra.The peak shifts reveal the interaction between PVP and the metal species.The interaction between PVP and metal precursors has effect on the formation of the colloidal metal nanoparticles.Strength of the intera...

Fabrication and Thermal Conductivity Improvement of Novel Composite Adsorbents adding with Nanoparticles

Thermal conductivity is one of key parameters of adsorbents, which will affect the overall system performance of adsorption chiller. To improve adsorbent＇s thermal conductivity is always one of research focuses in chemisorption field. A new chemical composite adsorbent is fabricated by adding carbon coated metal（Aluminum and Nickel） nanoparticles with three different addition amounts into the mixture of chloride salts and natural expanded graphite aiming to improve the thermal conductivity. The preparation processes and its thermal conductivity of this novel composite adsorbent are reported and summarized. Experimental results indicate that the nanoparticles are homogenously dispersed in the composite adsorbent by applying the reported preparation processes. The thermal conductivity of the composite adsorbent can averagely enlarge by 20% when the weight ratio of the added nanoparticles is 10 wt%. Moreover, carbon coated aluminum nanoparticles exhibit more effective enlargement in thermal conductivity than nickel nanoparticles. As for the composite adsorbent of CaCl2-NEG, there is a big reinforcement from 30% to 50% for Al@C nanoparticles, however only 10% in maximum caused by Ni@C nanoparticles. The proposed research provides a methodology to design and prepare thermal conductive chemical composite adsorbent.

CATALYTIC PROPERTIES OF POLYMER-STABILIZED COLLOIDAL METAL NANOPARTICLES SYNTHESIZED BY MICROWAVE IRRADIATION

Catalytic properties of polymer-stabilized colloidal metal nanoparticles synthesized by microwave irradiationwere studied in the selective hydrogenation of unsaturated aldehydes,o-chloronitrobenzene and the hydrogenationof alkenes.The results show that nanosized metal particles synthesized by microwave irradiation have similar catalyticperformance in selective hydrogenation of unsaturated aldehydes,better selectivity to o-chloroaniline in hydrogenation ofo-chloronitrobenzene and higher catalytic activities in hydrogenation of alkenes,compared with metal clusters prepared byconventional heating.The same apparent activation energy(E_a=29 kJ mol^(-(?)) for hydrogenation of (?)-heptene catalyzed withplatinum nanoparticles prepared by both heating modes implied that the reaction followed the same mechanism.

Sustainable solid-state synthesis of uniformly distributed PdAg alloy nanoparticles for electrocatalytic hydrogen oxidation and evolution

New sustainable syntheses based on solid-state strategies have sparked enormous attention and provided novel routes for the synthesis of supported metallic alloy nanocatalysts(SMACs).Despite considerable recent progress in this field,most of the developed methods suffer from either complex operations or poorly controlled morphology,which seriously limits their practical applications.Here,we have developed a sustainable strategy for the synthesis of PdAg alloy nanoparticles(NPs)with an ultrafine size and good dispersion on various carbon matrices by directly grinding the precursors in an agate mortar at room temperature.Interestingly,no solvents or organic reagents are used in the synthesis procedure.This simple and green synthesis procedure provides alloy NPs with clean surfaces and thus an abundance of accessible active sites.Based on the combination of this property and the synergistic and alloy effects between Pd and Ag atoms,which endow the NPs with high intrinsic activity,the PdAg/C samples exhibit excellent activities as electrocatalysts for both the hydrogen oxidation and evolution reactions(HOR and HER)in a basic medium.Pd9Ag1/C showed the highest activity in the HOR with the largest j0,m value of 26.5 A g Pd^–1 and j0,s value of 0.033 mA cmPd^–2,as well as in the HER,with the lowest overpotential of 68 mV at 10 mA cm^–2.As this synthetic method can be easily adapted to other systems,the present scalable solid-state strategy may open opportunity for the general synthesis of a wide range of well-defined SMACs for diverse applications.

Thermodynamic analysis and modification of Gibbs–Thomson equation for melting point depression of metal nanoparticles

Abnormal melting point depression of metal nanoparticles often occurs in heterogeneous catalytic reactions,which leads to a reduction in the stability of reactive nanoclusters.To study this abnormal phenomenon,the original and surface-energy modified Gibbs-Thomson equations were analyzed in this work and further modified by considering the effect of the substrate.The results revealed that the original Gibbs-Thomson equation was not suitable for the particles with radii smaller than 10 nm.Moreover,the performance of the surface-energy modified Gibbs-Thomson equation was improved,and the deviation was reduced to(-350-100)K,although further modification of the equation by considering the interfacial effect was necessary for the small particles(r<5 nm).The new model with the interfacial effect improved the model performance with a deviation of approximately-50 to 20 K,where the interfacial effect can be predicted quantitatively from the thermodynamic properties of the metal and substrate.Additionally,the micro-wetting parameterα_W can be used to qualitatively study the overall impact of the substrate on the melting point depression.

Second harmonic generation of metal nanoparticles under tightly focused illumination

The near-field and far-field second harmonic （SH） responses of a metal spherical nanoparticle placed in the focal region of a highly focused beam are investigated by using the calculation model based on three-dimensional finite-difference time-domain （FDTD） method. The results show that off-axis backward-propagating SH response can be reinforced by tightly focusing, due to the increase of the relative magnitude of the longitudinal field component and the phase shift along the propagation direction.

Onion-structured transition metal dichalcogenide nanoparticles by laser fabrication in liquids and atmospheres

Since the discovery of transition metal dichalcogenide(TMDC)nanoparticles(NPs)with the onion-like structure,many efforts have been made to develop their fabrication methods.Laser fabrication(LF)is one of the most promising methods to prepare onion-structured TMDC(or OS-TMDC)NPs due to its green,flexible,and scalable syntheses.In this mini-review article,we systematically introduce various laser-induced OS-TMDC(especially the OS-MoS_(2))NPs,their formation mechanism,properties,and applications.The preparation routes mainly include laser ablation in liquids and atmospheres,and laser irradiation in liquids.The various formation mechanisms are then introduced based on the different preparation routes,to describe the formations of the corresponding OS-NPs.Finally,some interesting properties and novel applications of these NPs are briefly demonstrated,and a short outlook is also given.This review could help to understand the progress of the laser-induced OS-TMDC NPs and their applications.