Binder-Free MOF-Based and MOF-Derived Nanoarrays for Flexible Electrochemical Energy Storage: Progress and Perspectives.

The fast development of Internet of Things and the rapid advent of next-generation versatile wearable electronics require cost-effective and highly-efficient electroactive materials for flexible electrochemical energy storage devices. Among various electroactive materials, binder-free nanostructured arrays have attracted widespread attention. Featured with growing on a conductive and flexible substrate without using inactive and insulating binders, binder-free 3D nanoarray electrodes facilitate fast electron/ion transportation and rapid reaction kinetics with more exposed active sites, maintain structure integrity of electrodes even under bending or twisted conditions, readily release generated joule heat during charge/discharge cycles and achieve enhanced gravimetric capacity of the whole device. Binder-free metal-organic framework (MOF) nanoarrays and/or MOF-derived nanoarrays with high surface area and unique porous structure have emerged with great potential in energy storage field and been extensively exploited in recent years. In this review, common substrates used for binder-free nanoarrays are compared and discussed. Various MOF-based and MOF-derived nanoarrays, including metal oxides, sulfides, selenides, nitrides, phosphides and nitrogen-doped carbons, are surveyed and their electrochemical performance along with their applications in flexible energy storage are analyzed and overviewed. In addition, key technical issues and outlooks on future development of MOF-based and MOF-derived nanoarrays toward flexible energy storage are also offered.

Surface Structure Engineering of PdAg Alloys with Boosted CO2 Electrochemical Reduction Performance.

Converting carbon dioxide into high-value-added formic acid as a basic raw material for the chemical industry via an electrochemical process under ambient conditions not only alleviates greenhouse gas effects but also contributes to effective carbon cycles. Unfortunately, the most commonly used Pd-based catalysts can be easily poisoned by the in situ formed minor byproduct CO during the carbon dioxide reduction reaction (CRR) process. Herein, we report a facile method to synthesize highly uniformed PdAg alloys with tunable morphologies and electrocatalytic performance via a simple liquid synthesis approach. By tuning the molar ratio of the Ag+ and Pd2+ precursors, the morphologies, composition, and electrocatalytic activities of the obtained materials were well-regulated, which was characterized by TEM, XPS, XRD, as well as electrocatalytic measurements. The CRR results showed that the as-obtained Pd3Ag exhibited the highest performance among the five samples, with a faradic efficient (FE) of 96% for formic acid at -0.2 V (vs. reference hydrogen electrode (RHE)) and superior stability without current density decrease. The enhanced ability to adsorb and activate CO2 molecules, higher resistance to CO, and a faster electronic transfer speed resulting from the alloyed PdAg nanostructure worked together to make great contributions to the improvement of the CRR performance. These findings may provide a new feasible route toward the rational design and synthesis of alloy catalysts with high stability and selectivity for clean energy storage and conversion in the future.

Piezoelectric Property of Electrospun PVDF Nanofibers as Linking Tips of Artificial-Hair-Cell Structures in Cochlea.

The death of hair cells and damage of natural tip links is one of the main causes of hearing-loss disability, and the development of an advanced artificial hearing aid holds the key to assisting those suffering from hearing loss. This study demonstrates the potential of using electrospun polyvinylidene fluoride (PVDF) fibers to serve as the artificial tip links, for long-term hearing-aid-device development based on their piezoelectric properties. We have shown that the electrospun PVDF-fiber web, consisting of fibers ranging from 30-220 nm in diameter with high ß-phase content, possesses the high piezoresponse of 170 mV. Analyses based on combined characterization methods including SEM, TEM, XRD, FTIR, Raman, DSC, XPS, PFM and piezoelectricity have confirmed that an optimized value of 15 wt.% PVDF could act as an effective candidate for a tip-link connector in a vibration-frequency prototype. Based on this easily reproducible electrospinning technique and the multifunctionalities of the resulting PVDF fibers, this fundamental study may shed light on the bio-inspired design of artificial, self-powered, high performance, hair-cell-like sensors in cochlea to tackle the hearing loss issue.

Bimetallic Co-Mo sulfide/carbon composites derived from polyoxometalate encapsulated polydopamine-decorated ZIF nanocubes for efficient hydrogen and oxygen evolution.

The increased call for carbon neutrality by 2050 makes it compelling to develop emission-free alternative energy sources. Green hydrogen produced from water electrolyzers using renewable electricity is of great importance, and the development of efficient transition-metal-based materials for hydrogen production by electrolysis is highly desirable. In this report, a new approach to produce defect-rich and ultra-fine bimetallic Co-Mo sulfides/carbon composites from polyoxometalates@ZIF-67@polydopamine nanocubes via carbonization/sulfurization, which are highly active for hydrogen and oxygen evolution reactions (HER and OER), have been successfully developed. The coating of polydopamine (PDA) on the surface of the acid-sensitive ZIF-67 cubes can prevent the over-dissociation of ZIF-67 caused by the encapsulated phosphomolybdic acid (PMA) etching through PDA chelating with the PMA molecules. Meanwhile, the partially dissociated Co2+ from ZIF-67 can be captured by the coated PDA via chelation, resulting in more evenly dispersed active sites throughout the heterogeneous composite after pyrolysis. The optimized bimetallic composite CoMoS-600 exhibits a prominent improvement in HER (with an overpotential of -0.235 V vs. RHE at a current density of 10 mA cm-2) and OER performance (with an overpotential of 0.350 V vs. RHE at a current density of 10 mA cm-2), due to the synergistic effect of ultra-fine defect-rich Co-Mo-S nanoparticle active sites and N,S-codoped porous carbons in the composites. Moreover, this synthesis approach can be readily expanded to other acidic polyoxometalates to produce HER and OER active bimetallic Co-W sulfide/carbon composites by replacing PMA with phosphotungstic acid. This new synthesis strategy to modify acid-sensitive ZIFs with selected compounds offers an alternative approach to develop novel transition metal sulfide/carbon composites for various applications.

Recent Advances in Metal-Organic Frameworks Derived Nanocomposites for Photocatalytic Applications in Energy and Environment.

Solar energy is a key sustainable energy resource, and materials with optimal properties are essential for efficient solar energy-driven applications in photocatalysis. Metal-organic frameworks (MOFs) are excellent platforms to generate different nanocomposites comprising metals, oxides, chalcogenides, phosphides, or carbides embedded in porous carbon matrix. These MOF derived nanocomposites offer symbiosis of properties like high crystallinities, inherited morphologies, controllable dimensions, and tunable textural properties. Particularly, adjustable energy band positions achieved by in situ tailored self/external doping and controllable surface functionalities make these nanocomposites promising photocatalysts. Despite some progress in this field, fundamental questions remain to be addressed to further understand the relationship between the structures, properties, and photocatalytic performance of nanocomposites. In this review, different synthesis approaches including self-template and external-template methods to produce MOF derived nanocomposites with various dimensions (0D, 1D, 2D, or 3D), morphologies, chemical compositions, energy bandgaps, and surface functionalities are comprehensively summarized and analyzed. The state-of-the-art progress in the applications of MOF derived nanocomposites in photocatalytic water splitting for H2 generation, photodegradation of organic pollutants, and photocatalytic CO2 reduction are systemically reviewed. The relationships between the nanocomposite properties and their photocatalytic performance are highlighted, and the perspectives of MOF derived nanocomposites for photocatalytic applications are also discussed.

A generic method to synthesise graphitic carbon coated nanoparticles in large scale and their derivative polymer nanocomposites.

A versatile Rotary Chemical Vapour Deposition (RCVD) technique for the in-situ synthesis of large scale carbon-coated non-magnetic metal oxide nanoparticles (NPs) is presented, and a controllable coating thickness varying between 1-5 nm has been achieved. The technique has significantly up-scaled the traditional chemical vapour deposition (CVD) production for NPs from mg level to 10 s of grams per batch, with the potential for continuous manufacturing. The resulting smooth and uniform C-coatings sheathing the inner core metal oxide NPs are made of well-crystallised graphitic layers, as confirmed by electron microscopy imaging, electron dispersive spectrum elemental line scan, X-ray powder diffractions and Raman spectroscopy. Using nylon 12 as an example matrix, we further demonstrate that the inclusion of C-coated composite NPs into the matrix improves the thermal conductivity, from 0.205 W∙m-1∙K-1 for neat nylon 12 to 0.305 W∙m-1∙K-1 for a 4 wt% C-coated ZnO composite, in addition to a 27% improvement in tensile strength at 2 wt% addition.

Tracing the Bioavailability of Three-Dimensional Graphene Foam in Biological Tissues.

Graphene-based materials with a three-dimensional (3D) framework have been investigated for a variety of biomedical applications because of their 3D morphology, excellent physiochemical properties, volume stability, and their controllable degradation rate. Current knowledge on the toxicological implications and bioavailability of graphene foam (GF) has major uncertainties surrounding the fate and behavior of GF in exposed environments. Bioavailability, uptake, and partitioning could have potential effects on the behavior of GF in living organisms, which has not yet been investigated. Here, we report a pilot toxicology study on 3D GF in common carps. Our results showed that GF did not show any noticeable toxicity in common carps, and the antioxidant enzymatic activities, biochemical and blood parameters persisted within the standard series. Further histological imaging revealed that GF remained within liver and kidney macrophages for 7 days without showing obvious toxicity. An in vivo study also demonstrated a direct interaction between GF and biological systems, verifying its eco-friendly nature and high biocompatibility.

How the Toughest Inorganic Fullerene Cages Absorb Shockwave Pressures in a Protective Nanocomposite: Experimental Evidence from Two In Situ Investigations.

Nanocomposites fabricated using the toughest caged inorganic fullerene WS2 (IF-WS2) nanoparticles could offer ultimate protection via absorbing shockwaves; however, if the IF-WS2 nanomaterials really work, how they behave and what they experience within the nanocomposites at the right moment of impact have never been investigated effectively, due to the limitations of existing investigation techniques that are unable to elucidate the true characteristics of high-speed impacts in composites. We first fabricated Al matrix model nanocomposites and then unlocked the exact roles of IF-WS2 in it at the exact moment of impact, at a time resolution that has never been attempted before, using two in situ techniques. We find that the presence of IF-WS2 reduced the impact velocity by over 100 m/s and in pressure by at least 2 GPa against those Al and hexagonal WS2 platelet composites at an impact speed of 1000 m/s. The IF-WS2 composites achieved an intriguing inelastic impact and outperformed other reference composites, all originating from the "balloon effect" by absorbing the shockwave pressures. This study not only provides fundamental understanding for the dynamic performance of composites but also benefits the development of protective nanocomposite engineering.

Metal-organic-frameworks derived cobalt embedded in various carbon structures as bifunctional electrocatalysts for oxygen reduction and evolution reactions.

A series of nanocomposites of cobalt embedded in N-doped nanoporous carbons, carbon nanotubes or hollow carbon onions have been synthesized by a one-step carbonization of metal-organic-framework ZIF-67. The effect of the carbonization temperature on the structural evolution of the resulting nanocomposites has been investigated in detail. Among the as-synthesized materials, the cobalt/nanoporous N-doped carbon composites have demonstrated excellent electrocatalytic activities and durability towards oxygen reduction reaction in alkaline medium. Compared to the benchmark Pt/C catalyst, the optimized Co@C-800 (carbonized at 800 °C) exhibited high oxygen reduction reaction activity with an onset potential of 0.92 V, and a half-wave potential of 0.82 V. Moreover, the optimized Co@C-800 also showed enhanced electrocatalytic activity towards oxygen evolution reaction from water splitting, with a low onset potential of 1.43 V and a potential of 1.61 V at 10 mA cm-2 current density. This work offered a simple solution to develop metal-organic-framework-derived materials for highly efficient electrochemical applications.

Black-colored ZnO nanowires with enhanced photocatalytic hydrogen evolution.

Black-colored ZnO nanowires have been prepared in a metal-organic chemical vapor deposition system by employing a relatively low growth temperature and oxygen-deficient conditions. X-ray photoelectron spectroscopy reveals the incorporation of carbon into the nanowires. The photocatalytic hydrogen evolution activity of the black-colored ZnO nanowires is over 2.5 times larger than that of the pristine ZnO nanowires under simulated solar illumination conditions, and the enhanced photocatalytic activity can be attributed to the higher absorption of visible light by the black color and better carrier separation at the ZnO/carbon interface.

From graphene to silicon carbide: ultrathin silicon carbide flakes.

This study presents a new ultrathin SiC structure prepared by a catalyst free carbothermal method and post-sonication process. We have found that merging ultra-light 3D graphene foam and SiO together at high temperature leads to the formation of a complex SiC structure consisting of 3D SiC foam covered with traditional 1D nanowires. Upon breaking off, the 3D SiC was confirmed to be made from 2D nanosheets. The resulting novel 2D SiC nanosheets/nanoflakes were thoroughly investigated by using optical microscope, SEM, EDS, TEM, STEM, AFM, and Raman, which verified the highly crystallised structure feature. AFM results revealed an average thickness of 2-3 nm and average size of 2 µm for the flakes. This new SiC structure could not only actualise SiC usage for nano-electronic devices but is also expected to open new applications as well.

Ultralight, Strong, Three-Dimensional SiC Structures.

Ultralight and strong three-dimensional (3D) silicon carbide (SiC) structures have been generated by the carbothermal reduction of SiO with a graphene foam (GF). The resulting SiC foams have an average height of 2 mm and density ranging between 9 and 17 mg cm(-3). They are the lightest reported SiC structures. They consist of hollow struts made from ultrathin SiC flakes and long 1D SiC nanowires growing from the trusses, edges, and defect sites between layers. AFM results revealed an average flake thickness of 2-3 nm and lateral size of 2 µm. In-situ compression tests in the scanning electron microscope (SEM) show that, compared with most of the existing lightweight foams, the present 3D SiC exhibited superior compression strengths and significant recovery after compression strains of about 70%.

Cobalt sulfide/N,S codoped porous carbon core-shell nanocomposites as superior bifunctional electrocatalysts for oxygen reduction and evolution reactions.

Exploring highly-efficient and low-cost bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) in the renewable energy area has gained momentum but still remains a significant challenge. Here we present a simple but efficient method that utilizes ZIF-67 as the precursor and template for the one-step generation of homogeneous dispersed cobalt sulfide/N,S-codoped porous carbon nanocomposites as high-performance electrocatalysts. Due to the favourable molecular-like structural features and uniform dispersed active sites in the precursor, the resulting nanocomposites, possessing a unique core-shell structure, high porosity, homogeneous dispersion of active components together with N and S-doping effects, not only show excellent electrocatalytic activity towards ORR with the high onset potential (around -0.04 V vs.-0.02 V for the benchmark Pt/C catalyst) and four-electron pathway and OER with a small overpotential of 0.47 V for 10 mA cm(-2) current density, but also exhibit superior stability (92%) to the commercial Pt/C catalyst (74%) in ORR and promising OER stability (80%) with good methanol tolerance. Our findings suggest that the transition metal sulfide-porous carbon nanocomposites derived from the one-step simultaneous sulfurization and carbonization of zeolitic imidazolate frameworks are excellent alternative bifunctional electrocatalysts towards ORR and OER in the next generation of energy storage and conversion technologies.

Tribological performance of Graphene/Carbon nanotube hybrid reinforced Al2O3 composites.

Tribological performance of the hot-pressed pure Al2O3 and its composites containing various hybrid contents of graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs) were investigated under different loading conditions using the ball-on-disc method. Benchmarked against the pure Al2O3, the composite reinforced with a 0.5 wt% GNP exhibited a 23% reduction in the friction coefficient along with a promising 70% wear rate reduction, and a hybrid reinforcement consisting of 0.3 wt.% GNPs + 1 wt.% CNTs resulted in even better performance, with a 86% reduction in the wear rate. The extent of damage to the reinforcement phases caused during wear was studied using Raman spectroscopy. The wear mechanisms for the composites were analysed based on the mechanical properties, brittleness index and microstructural characterizations. The excellent coordination between GNPs and CNTs contributed to the excellent wear resistance property in the hybrid GNT-reinforced composites. GNPs played the important role in the formation of a tribofilm on the worn surface by exfoliation; whereas CNTs contributed to the improvement in fracture toughness and prevented the grains from being pulled out during the tribological test.

Ultra-toughened nylon 12 nanocomposites reinforced with IF-WS2.

Inorganic fullerene-like WS2 nanoparticle- (IF-WS2) reinforced nylon 12 nanocomposites have been prepared through effective ultrasonic mixing without using any surfactant, followed by molding at 220 °C. Morphological characterizations using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and microcomputed tomography (micro-CT) have revealed the excellent dispersion of IF-WS2 nanoparticles in the nylon 12 matrix. X-ray diffraction (XRD) analyses have confirmed that a phase transition from α'-phase to a more stable γ-phase took place during the sintering of nylon 12, regardless of the amount of IF-WS2 added to the matrix. At a very low IF-WS2 content of 2 wt%, the tensile strength and bending strength of the composites increased slightly by 27% and 28%, respectively. However, the toughness dramatically improved by 185% and 148% at IF-WS2 additions of 0.25 and 0.5 wt%, respectively, when compared to the neat nylon 12. It is believed that such improvements should mainly be attributed to the well-dispersed IF-WS2 within the matrix. The vastly improved toughness suggests that the resulting polymer nanocomposites could be promising for structural and high-performance impact applications.

Multi-walled carbon/IF-WS2 nanoparticles with improved thermal properties.

A unique new class of core-shell structured composite nanoparticles, C-coated inorganic fullerene-like WS2 (IF-WS2) hollow nanoparticles, has been created for the first time in large quantities, by a continuous chemical vapour deposition method using a rotary furnace. Transmission electron microscopy and Raman characterisations of the resulting samples reveal that the composite nanoparticles exhibited a uniform shell of carbon coating, ranging from 2-5 nm on the IF-WS2 core, with little or no agglomeration. Importantly, thermogravimetric analysis and differential scanning calorimetry analysis confirm that their thermal stability against oxidation in air has been improved by about 70 °C, compared to the pristine IF-WS2, making these new C-coated IF-WS2 nanoparticles more attractive for critical engineering applications.

Patterned growth of tungsten oxide and tungsten oxynitride nanorods from Au-coated W foil.

This manuscript first describes a simple synthesis of tungsten oxide (WO(x)) nanorods from templated W foil using a chemical vapour deposition (CVD) technique at 600-750 °C, then presents the formation of tungsten oxynitride (WO(x)N(y)) nanorods via nitridation at 650 °C for different reaction times. The W foil, blade engraved, acid etched, or spin coated with Au-block copolymer composites then plasma etched, was used as a substrate for the nanorod growth. The Au patterns that were created on the surface of a W foil following the removal of the copolymer, led to a reverse patterned growth of WO(x) nanorods on the Au free areas. Consequently, following the oxide-to-nitride conversion, WO(x)N(y) nanorods were obtained with an identical patterned feature as to that of the parental WO(x). Combined techniques including XRD, SEM, TEM and Raman were used to visualise and analyse the resulting WO(x) and WO(x)N(y) nanorods. The diameter, length, and chemical composition of the nanorods are found to vary with reaction time and temperatures, as well as different substrate pre-treatments. This result represents a simple, innovative and efficient process for reverse-patterned growth of new nanomaterials.

Templated nanoscale porous carbons.

This manuscript reviews key developments in the important and rapidly expanding area of templated porous carbons. The porosity covered ranges from microporous to mesoporous and macroporous carbons. Two modes of templating, using so-called hard and soft templates, are covered. In particular, for hard templating, zeolite templating generates microporous carbons, mesoporous silicates yield mesoporous carbons, while colloidal particles are replicated to large mesoporous and macroporous carbons. Soft-templating, a more recent phenomenon, mainly generates mesoporous carbons. The full range of pore sizes can therefore now be accessed using hard and soft templates to generate highly ordered nanoscale carbons with well-defined and optimised textural properties. The research area has seen rapid and important developments over the last few years, and this review aims to present the more significant advances.

Hydrogen storage in high surface area carbons: experimental demonstration of the effects of nitrogen doping.

The influence of nitrogen doping on the hydrogen uptake and storage capacity of high surface area carbon materials is presented in this report. To generate suitable study materials, we have exploited the relationship between synthesis conditions and textural properties of zeolite-templated carbons to generate a range of high surface area carbons with similar pore size distribution but which are either N-doped or N-free. For N-doped carbons, the nitrogen content was kept within a narrow range of between 4.7 and 7.7 wt %. The carbon materials, irrespective of whether they were doped or not, exhibited high surface area (1900-3700 m(2)/g) and pore volume (0.99 and 1.88 cm(3)/g), a micropore surface area of 1500-2800 m(2)/g, and a micropore volume of 0.65-1.24 cm(3)/g. The hydrogen uptake varied between 4.1 and 6.9 wt %. We present experimental data that indicates that the effect of N-doping on hydrogen uptake is only apparent when related to the surface area and pore volume associated with micropores rather than total porosity. Furthermore, by considering the isosteric heat of hydrogen adsorption and excess hydrogen uptake on N-free or N-doped carbons, it is shown that N-doping can be beneficial at lower coverage (low hydrogen uptake) but is detrimental at higher coverage (higher hydrogen uptake). The findings are consistent with previous theoretical predictions on the effect of N-doping of carbon on hydrogen uptake. The findings, therefore, add new insights that are useful for the development of carbon materials with enhanced hydrogen storage capacity.

Bundled tungsten oxide nanowires under thermal processing.

Ultra-thin W(18)O(49) nanowires were initially obtained by a simple solvothermal method using tungsten chloride and cyclohexanol as precursors. Thermal processing of the resulting bundled nanowires has been carried out in air in a tube furnace. The morphology and phase transformation behavior of the as-synthesized nanowires as a function of annealing temperature have been characterized by x-ray diffraction and electron microscopy. The nanostructured bundles underwent a series of morphological evolution with increased annealing temperature, becoming straighter, larger in diameter, and smaller in aspect ratio, eventually becoming irregular particles with size up to 5 µm. At 500 °C, the monoclinic W(18)O(49) was completely transformed to monoclinic WO(3) phase, which remains stable at high processing temperature. After thermal processing at 400 °C and 450 °C, the specific surface areas of the resulting nanowires dropped to 110 m(2) g(-1) and 66 m(2) g(-1) respectively, compared with that of 151 m(2) g(-1) for the as-prepared sample. This study may shed light on the understanding of the geometrical and structural evolution occurring in nanowires whose working environment may involve severe temperature variations.