Emerging properties of non-crystalline phases of graphene and boron nitride based materials

We review recent developments on the synthesis and properties of two-dimensional materials which, although being mainly of an sp^(2) bonding character, exhibit highly disordered, non-uniform and structurally random morphologies. The emergence of such class of amorphous materials, including amorphous graphene and boron nitride, have shown superior properties compared to their crystalline counterparts when used as interfacial films. In this paper we discuss their structural,vibrational and electronic properties and present a perspective of their use for electronic applications.

Phase formation and thermoelectric properties of Zn_(1+x)Sb binary system

The phase formation and thermoelectric(TE)properties in the central region of the Zn−Sb phase diagram were analyzed through synthesizing a series of Zn_(1+x)Sb(x=0,0.05,0.1,0.15,0.25,0.3)materials by reacting Zn and Sb powders below the solidus line of the Zn−Sb binary phase diagram followed by furnace cooling.In this process,the nonstoichiometric powder blend crystallized in a combination of ZnSb andβ-Zn4Sb3 phases.Then,the materials were ground and hot pressed to form dense ZnSb/β-Zn4Sb3 composites.No traces of Sb and Zn elements or other phases were revealed by X-ray diffraction,high resolution transmission electron microscopy and electron energy loss spectroscopy analyses.The thermoelectric properties of all materials could be rationalized as a combination of the thermoelectric behavior of ZnSb andβ-Zn4Sb3 phases,which were dominated by the main phase in each sample.Zn1.3Sb composite exhibited the best thermoelectric performance.It was also found that Ge doping substantially increased the Seebeck coefficient of Zn1.3Sb and led to significantly higher power factor,up to 1.51 mW·m−1·K−2 at 540 K.Overall,an exceptional and stable TE figure of merit(ZT)of 1.17 at 650 K was obtained for Zn1.28Ge0.02Sb.

Additive engineering for stable halide perovskite solar cells

Halide perovskite solar cells(PSCs)have already demonstrated power conversion efficiencies above 25%,which makes them one of the most attractive photovoltaic technologies.However,one of the main bottlenecks towards their commercialization is their long-term stability,which should exceed the 20-year mark.Additive engineering is an effective pathway for the enhancement of device lifetime.Additives applied as organic or inorganic compounds,improve crystal grain growth enhancing power conversion efficiency.The interaction of their functional groups with the halide perovskite(HP)absorber,as well as with the transport layers,results in defect passivation and ion immobilization improving device performance and stability.In this review,we briefly summarize the different types of additives recently applied in PSC to enhance not only efficiency but also long-term stability.We discuss the different mechanism behind additive engineering and the role of the functional groups of these additives for defect passivation.Special emphasis is given to their effect on the stability of PSCs under environmental conditions such as humidity,atmosphere,light irradiation(UV,visible)or heat,taking into account the recently reported ISOS protocols.We also discuss the relation between deep-defect passivation,non-radiative recombination and device efficiency,as well as the possible relation between shallow-defect passivation,ion immobilization and device operational stability.Finally,insights into the challenge and criteria for additive selection are provided for the further stability enhancement of PSCs.

Toward integrated detection and graphene-based removal of contaminants in a lab-on-a-chip platform

A novel miniaturized microfluidic platform was developed for the simultaneous detection and removal of polybrominated diphenyl ethers （PBDEs）. The platform consists of a polydimethylsiloxane （PDMS） microfluidic chip for an immunoreaction step, a PDMS chip with an integrated screen-printed electrode （SPCE） for detection, and a PDMS-reduced graphene oxide （rGO） chip for physical adsorption and subsequent removal of PBDE residues. The detection was based on competitive immunoassay-linked binding between PBDE and PBDE modified with horseradish peroxidase （HRP-PBDE） followed by the monitoring of enzymatic oxidation of o-aminophenol （o-AP） using square wave anodic stripping voltammetry （SW-ASV）. PBDE was detected with good sensitivity and a limit of detection similar to that obtained with a commercial colorimetric test （0.018 ppb）, but with the advantage of using lower reagent volumes and a reduced analysis time. The use of microfluidic chips also provides improved linearity and a better reproducibility in comparison to those obtained with batch-based measurements using screen-printed electrodes. In order to design a detection system suitable for toxic compounds such as PBDEs, a reduced graphene oxide-PDMS composite was developed and optimized to obtain increased adsorption （based on both the hydrophobicity and rr-v~ stacking between rGO and PBDE molecules） compared to those of non-modified PDMS. To the best of our knowledge, this is the first demonstration of electrochemical detection of flame retardants and a novel application of the rGO-PDMS composite in a biosensing system. This system can be easily applied to detect any analyte using the appropriate immunoassay and it supports operation in complex matrices such as seawater.

Local and correlated studies of humidity-mediated ferroelectric thin film surface charge dynamics

Electrochemical phenomena in ferroelectrics are of particular interest for catalysis and sensing applications,with recent studies highlighting the combined role of the ferroelectric polarisation,applied surface voltage and overall switching history.Here,we present a systematic Kelvin probe microscopy study of the effect of relative humidity and polarisation switching history on the surface charge dissipation in ferroelectric Pb(Zr_(0.2)Ti_(0.8))O_(3)thin films.We analyse the interaction of surface charges with ferroelectric domains through the framework of physically constrained unsupervised machine learning matrix factorisation,Dictionary Learning,and reveal a complex interplay of voltage-mediated physical processes underlying the observed signal decays.Additional insight into the observed behaviours is given by a Fitzhugh–Nagumo reaction–diffusion model,highlighting the lateral spread and charge passivation process contributors within the Dictionary Learning analysis.

Angular dependence of nanoparticle generation in the matrix assembly cluster source

The matrix assembly cluster source(MACS)represents a bridge between conventional instruments for cluster beam deposition(CBD)and thelevel of industrial production.The method is based on Ar^+ion sputtering of a pre-condensed Ar-M matrix(where M,is typically a metal such asAg).Each Ar^+ion produces a collision cascade and thus the formation of metal clusters is in the matrix,which are then sputtered out.Here wepresent an experimental and computational investigation of the cluster emission process,specifically its dependence on the Ar^+ion angle of in cidence and the cluster emission angle.We find the in cide nee angle strongly in flue nces the emerging cluster flux,which is assigned to thespatial location of the deposited primary ion energy relative to the cluster into the matrix.We also found an approximately constant anglebetween the incident ion beam and the peak in the emitted cluster distribution,with value between 99°and 109°.

Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks:The case of squaramide

A well-established strategy to synthesize heterogeneous,metal-organic framework(MOF)catalysts that exhibit nanoconfinement effects,and specific pores with highly-localized catalytic sites,is to use organic linkers containing organocatalytic centers.Here,we report that by combining this linker approach with reticular chemistry,and exploiting three-dimensioanl(3D)MOF-structural data from the Cambridge Structural Database,we have designed four heterogeneous MOF-based catalysts for standard organic transformations.These programmable MOFs are isoreticular versions of pcu IRMOF-16,feu UiO-68 and pillared-pcu SNU-8X,the three most common topologies of MOFs built from the organic linker p.p'-terphenyldicarboxylic acid(tpdc).To synthesize the four squaramide-based MOFs,we designed and synthesized a linker,4,4’-((3,4-dioxocyclobut-1-ene-1,2-diyl)bis(azanedyil))dibenzoic acid(Sq_tpdc),which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers.Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena.Therefore,the four MOFs share the same organocatalytic squaramide moiety,but confine it within distinct pore environments.We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations:a Friedel-Crafts alkylation and an epoxide ring-opening.Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.

Bioluminescent nanopaper for rapid screening of toxic substances

Environmental pollution is threatening human health and ecosystems as a result of modern agricultural techniques and industrial progress. A simple nanopaper-based platform coupled with luminescent bacteria Aliivibrio Jischeri （A. Jischeri） as a bio-indicator is presented here, for rapid and sensitive evaluation of contaminant toxicity. When exposed to toxicants, the luminescence inhibition of A. Jischeri-decorated bioluminescent nanopaper （BLN） can be quantified and analyzed to classify the toxicity level of a pollutant. The BLN composite was characterized in terms of morphology and functionality. Given the outstanding biocompatibility of nanocellulose for bacterial proliferation, BLN achieved high sensitivity with a low cost and simplified procedure compared to conventional instruments for laboratory use only. The broad applicability of BLN devices to environmental samples was studied in spiked real matrices （lake and sea water）, and their potential for direct and in situ toxicity screening was demonstrated. The BLN architecture not only survives but also maintains its function during freezing and recycling processes, endowing the BLN system with competitive advantages as a deliverable, ready-to-use device for large-scale manufacturing. The novel luminescent bacteria-immobilized, nanocelullose-based device shows outstanding abilities for toxicity bioassays of hazardous compounds, bringing new possibilities for cheap and efficient environmental monitoring of potential contamination.

Milliwatt terahertz harmonic generation from topological insulator metamaterials

Achieving effcient,high-power harmonic generation in the terahertz spectral domain has technological applications,for example,in sixth generation(6G)communication networks.Massless Dirac fermions possess extremely large terahertz nonlinear susceptibilities and harmonic conversion effciencies.However,the observed maximum generated harmonic power is limited,because of saturation effects at increasing incident powers,as shown recently for graphene.Here,we demonstrate room-temperature terahertz harmonic generation in a Bi_(2)Se_(3) topological insulator and topological-insulator-grating metamaterial structures with surface-selective terahertz field enhancement.We obtain a third-harmonic power approaching the miliwatt range for an incident power of 75 mW-an improvement by two orders of magnitude compared to a benchmarked graphene sample.We establish a framework in which this exceptional performance is the result of thermodynamic harmonic generation by the massless topological surface states,benefiting from ultrafast dissipation of electronic heat via surface-bulk Coulomb interactions.These results are an important step towards on-chip terahertz(opto)electronic applications.

Graphene quantum dots: From efficient preparation to safe renal excretion

Carbon nanomaterials offer excellent prospects as therapeutic agents,and among them,graphene quantum dots(GQDs)have gained considerable interest thanks to their aqueous solubility and intrinsic fluorescence,which enable their possible use in theranostic approaches,if their biocompatibility and favorable pharmacokinetic are confirmed.We prepared ultra-small GQDs using an alternative,reproducible,top-down synthesis starting from graphene oxide with a nearly 100%conversion.The materials were tested to assess their safety,demonstrating good biocompatibility and ability in passing the ultrafiltration barrier using an in vitro model.This leads to renal excretion without affecting the kidneys.Moreover,we studied the GQDs in vivo biodistribution confirming their efficient renal clearance,and we demonstrated that the internalization mechanism into podocytes is caveolae-mediated.Therefore,considering the reported characteristics,it appears possible to vehiculate compounds to kidneys by means of GQDs,overcoming problems related to lysosomal degradation.

Waste Tire Rubber-based Refrigerants for Solid-state Cooling Devices

Management of discarded tires is a compelling environmental issue worldwide.Although there are several approaches developed to recycle waste tire rubbers,their application in solid-state cooling is still unexplored.Considering the high barocaloric potential verified for elastomers,the use of waste tire rubber(WTR)as a refrigerant in solid-state cooling devices is very promising.Herein,we investigated the barocaloric effects in WTR and polymer blends made of vulcanized natural rubber(VNR)and WTR,to evaluate its feasibility for solid-state cooling technologies.The adiabatic temperature changes and the isothermal entropy changes reach giant values,as well as the performance parameters,being comparable or even better than most barocaloric materials in literature.Moreover,pure WTR and WTR-based samples also present a faster thermal exchange than VNR,consisting of an additional advantage of using these discarded materials.Thus,the present findings evidence the encouraging perspectives of employing waste rubbers in solid-state cooling based on barocaloric effects,contributing to both the recycling of polymers and the sustainable energy technology field.

Large edge magnetism in oxidized few-layer black phosphorus nanomeshes

The formation and control of a room-temperature magnetic order in two- dimensional （2D） materials is a challenging quest for the advent of innovative magnetic- and spintronic-based technologies. To date, edge magnetism in 2D materials has been experimentally observed in hydrogen （H）-terminated graphene nanoribbons （GNRs） and graphene nanomeshes （GNMs）, but the measured magnetization remains far too small to allow envisioning practical applications. Herein, we report experimental evidences of large room-temperature edge ferromagnetism （FM） obtained from oxygen （O）-terminated zigzag pore edges of few-layer black phosphorus （P） nanomeshes （BPNMs）. The magnetization values per unit area are -100 times larger than those reported for H-terminated GNMs, while the magnetism is absent for H-terminated BPNMs. The magnetization measurements and the first-principles simulations suggest that the origin of such a magnetic order could stem from ferromagnetic spin coupling between edge P with O atoms, resulting in a strong spin localization at the edge valence band, and from uniform oxidation of full pore edges over a large area and interlayer spin interaction. Our findings pave the way for realizing high-efficiency 2D flexible magnetic and spintronic devices without the use of rare magnetic elements.

The elphbolt ab initio solver for the coupled electron-phonon Boltzmann transport equations

elphbolt is a modern Fortran (2018 standard) code for efficiently solving the coupled electron–phonon Boltzmann transport equations from first principles.Using results from density functional and density functional perturbation theory as inputs,it can calculate the effect of the non-equilibrium phonons on the electronic transport (phonon drag) and non-equilibrium electrons on the phononic transport (electron drag) in a fully self-consistent manner and obeying the constraints mandated by thermodynamics.It can calculate the lattice,charge,and thermoelectric transport coefficients for the temperature gradient and electric fields,and the effect of the mutual electron–phonon drag on these transport properties.The code fully exploits the symmetries of the crystal and the transport-active window to allow the sampling of extremely fine electron and phonon wave vector meshes required for accurately capturing the drag phenomena.The coarray feature of modern Fortran,which offers native and convenient support for parallelization,is utilized.The code is compact,readable,well-documented,and extensible by design.