Bioprocess-inspired Actin Biomineralized Hematite Mesocrystals for Energy Storage

Biomineralization is a biological process of synthesizing inorganic minerals within organisms.It has been found that intracellular proteins are involved in the room temperature synthesis process of anatase Ti O2in living mussels.Here,we used intracellular actin to synthesize hematite by biomineralization.Biomineralized hematite has a nano spindle structure with a particle size of approximately 150 nm.The microstructure indicates that the prepared hematite is a mesocrystals composed of ordered arrangement and assembly of primary nanoparticles.In addition,hematite mesocrystals exhibit good lithium storage performance as electrode materials for lithium batteries.The discharge specific capacity of the battery remained at 560.7 m Ah·g^(-1)after 130 cycles at a current density of 200 m A·g^(-1).This work expands the synthesis methods of hematite by biomineralization,and provides a new strategy for preparing inorganic materials by intracellular proteins.

Development of tailored TiO_2 mesocrystals for solar driven photocatalysis

Ordered metal oxides superstructures have attracted much more attention in the fields of fuel generation and environmental purification owing to their unique physiochemical characteristics such as large surface area, fine pore structure, efficient electronic mobility, and good stability. Very recently, TiOmesocrystals（TMCs） having superstructures self-assembled by TiOnanoparticle building blocks, are of considerable interest in current research and application ranging from UV to visible light attributed to their efficient charge separation and superior photocatalytic activity. In this review, we describe the common procedures to prepare unique TMCs and overview of recent developments of TMCs during last 3 years, especially the structure-related or electronic-effected mechanism in photocatalytic reaction. Further, we introduce the characterization and fundamental properties of modified TMCs by the means of single-particle fluorescence microscopy for unraveling the charge transport and photocatalytic properties of individual TMCs and time-resolved diffuse reflectance spectroscopy（TDR） for monitoring the charge transfer dynamics. Finally, various aspects on TMCs are discussed for the future developments of energy and environmental fields.

TiO_2 mesocrystals: Synthesis, formation mechanisms and applications

Mesocrystals, which are assemblies of crystallographically oriented nanocrystals, have received increasing attention due to their unique properties such as high crystallinity, high porosity, oriented subunit alignment, and similarity to highly sophisticated biominerals. However, the controlled synthesis of TiO 2 mesocrystals has not been realized until recently, probably because of the difficulty in accurately controlling the reaction processes that produce TiO 2 crystals. In this review, recent advances in the synthesis and applications of TiO 2 mesocrystals are summarized with particular attention paid to the mechanisms of their formation. Three typical pathways for the preparation of TiO 2 mesocrystals are discussed, namely topotactic transformation, direct synthesis in solution, and growth on supports. The potential applications of TiO 2 mesocrystals in lithium ion batteries, photocatalysis, enzyme immobilization, and antireflection materials are also described.

Enhanced Photocatalytic Activity of Z-scheme Meso-BiVO_(4)-Au-CdS for Degradation of Rhodamine B

We synthesized BiVO_(4)mesocrystals with ordered assembly structure,and studied the structural order and the relationship between the photodegradation of Rhodamine B.Au nanoparticles(NPs)were successfully loaded onto Meso-BiVO_(4)by light-assisted induction,and Cd nanoparticles were further selected to be deposited on Au nanoparticles to form Z-scheme photocatalyst Meso-BiVO_(4)-Au-CdS heterostructures.We try and propose to analyze its ordered assembly structure by XRD for the first time.The results show that Meso-BiVO_(4)is a mesocrystal with highly exposed(001)plane and directional assembly structure.The charge separation efficiency of all samples was studied by PL spectroscopy.The results show that the Z-scheme Meso-BiVO_(4)-Au-CdS can promote the charge separation and obtain the best carrier separation efficiency.Thus,it has the best photocatalytic activity in the experiment of photocatalytic degradation of rhodamine B.The main active species in the degradation process were confirmed by free radical trapping experiment,and the degradation mechanism was put forward.

Metal oxide mesocrystals and mesoporous single crystals:synthesis,properties and applications in solar energy conversion

Metal oxide mesocrystals(MCs)and mesoporous single crystals(MSCs)exhibit superior carrier transport ability,high specific surface area,shortened photo-carrier diffusion lengths to interfaces and enhanced absorbance of the incident sunlight.These advanced features make metal oxide MCs and MSCs be a promising candidate material in photocatalysis,photoelectrocatalysis,dye sensitized solar cells(DSSCs)and perovskite solar cells(PSCs).Recently,remarkable advances of applying metal oxide MCs and MSCs in these areas have been achieved.Therefore,it is extremely important to deeply understand the influence of the unique properties of metal oxide MCs and MSCs on solar energy conversion systems.Herein,we presented a brief introduction on the synthesis and carrier transfer behavior of metal oxide MCs and MSCs.Then,the rational structure design and modification of metal oxide MCs and MSCs for photocatalysis,photoelectrocatalysis,DSSCs and PSCs are systematically discussed.Finally,the perspectives on extending the application of metal oxide MCs and MSCs are addressed.

Formation of magnesium calcite mesocrystals in the inorganic environment only by using Ca^(2+)and Mg^(2+)and its biological implications

Magnesium calcite(Mg-calcite)mesocrystal is widespread in the biominerals with specific functions.Until now,it remains challenging to obtain Mg-calcite mesocrystals without organic additives and the formation mechanism of Mg-calcite mesocrystals in the ocean is not clear yet.We report here the synthesis of corn-like Mg-calcite mesocrystals from pure amorphous calcium carbonate(ACC)via a facile method only by using Ca^(2+)and Mg^(2+).The obtained Mg-calcite is composed of many nanocubes with common crystallographic orientation,which shows very good single crystal feature.In the crystallizing procedure,the ACC nanospheres rapidly agglomerate into Mg-calcite corn-like mesocrystal by oriented attachment(OA)in a certain direction,which belongs to the non-classical nucleation.By this method,the molar ratio of Ca^(2+)and Mg^(2+)plays a vital role in the whole crystallization procedure,which may shed a new light on disclosing the mechanism behind for the effect of seawater in the formation of biological Mg-calcite in nature.

Self-supported yttria-stabilized zirconia mesocrystals with tunable mesopores prepared by a chemi-thermal process

Mesoporous mesocrystals are highly desired in catalysis,energy storage,medical and many other applications,but most of synthesis strategies involve the usage of costly chemicals and complicated synthesis routes,which impede the commercialization of such materials.During the sintering of dense ceramics,coarsening is an undesirable phenomenon which causes the growth of the grains as well as the pores hence hinders the densification,however,coarsening is desired in the sintering of porous ceramics to expand the pore sizes while retaining the total pore volume.Here we report a chemi-thermal process,during which nanocrystallite aggregates were synthesized by hydrothermal process and then converted to the product by sintering.Through this strategy,we synthesized mesoporous self-supported mesocrystals of yttria-stabilized zirconia with tunable pore size and the process was then scaled-up to industrial production.The thermal conductivity measurement shows that the mesoporous powder is a good thermal isolator.The monolith pellets can be obtained by SPS sintering under high pressure and the mesoporosity is retained in the monolith pellets.This work features facile and scalable process as well as low cost raw chemicals making it highly desirable in industrial applications.

Hierarchical Silver Indium Tungsten Oxide Mesocrystals with Morphology-, Pressure-, and Temperature-Dependent Luminescence Properties

Highly hierarchical structures of silver indium tungsten oxide(AgIn(WO_(4))_(2))mesocrystals can be rationally fabricated via the microwave-assisted synthesis method by tuning the initial concentrations of the precursors.Photoluminescence spectra of hierarchical AgIn(WO_(4))_(2) mesocrystals were measured to investigate the correlation between the morphology,pressure,and temperature and their luminescence properties.The materials showed interesting white emission when excited by visible light of wavelength 460 nm.AgIn(WO_(4))_(2) materials having different morphologies displayed notable differences in photogenerated emission performance.The emission was strongly correlated with the surface nanostructures of outgrowths,with larger amounts of outgrowths leading to stronger emission intensities.The pressure-and temperature-dependent photoluminescence properties of these materials have also been investigated under hydrostatic pressures up to 16 GPa at room temperature and in the temperature range from 10 to 300 K.

Synthesis of TiO_2 mesocrystal film with enhanced photocatalytic activity

TiO2 mesocrystals can considerably enhance charge separation owing to their oriented superstructures,with fewer internal defects and porous properties providing more active sites.In this work,we prepared TiO2 mesocrystal films by a direct annealing method.The morphology and crystal phase of the film were controlled by adjusting the ratio of NH4F and the calcination temperature.Moreover,we found that Au nanoparticles loaded on a TiO2 mesocrystal film enabled highly efficient visible light photocatalytic properties.The photocatalytic activities were studied by hydrogen generation and photoreduction of Cr(VI).This work represents a considerable advance in the development and application of the TiO2 mesocrystals.

Nanocomposite superstructure of zinc oxide mesocrystal/reduced graphene oxide with effective photoconductivity

Metal oxide mesocrystals are the alignment of metal oxide nanoparticles building blocks into the ordered superstructure,which have potentially tunable optical,electronic,and electrical properties suitable for practical applications.Herein,we report an effective method for synthesizing mesocrystal zinc oxide nanorods(ZnONRs).The crystal,surface,and internal structures of the zinc oxide mesocrystals were fully characterized.Mesocrystal zinc oxide nanorods/reduced graphene oxide(ZnONRs/rGO)nanocomposite superstructure were synthesized also using the hydrothermal method.The crystal,surface,chemical,and internal structures of the ZnONRs/rGO nanocomposite superstructure were also fully characterized.The optical absorption coefficient,bandgap energy,band structure,and electrical conductivity of the ZnONRs/rGO nanocomposite superstructure were investigated to understand its optoelectronic and electrical properties.Finally,the photoconductivity of the ZnONRs/rGO nanocomposite superstructure was explored to find the possibilities of using this nanocomposite superstructure for ultraviolet(UV)photodetection applications.Finally,we concluded that the ZnONRs/rGO nanocomposite superstructure has high UV sensitivity and is suitable for UV detector applications.

Morphology control and shape evolution in 3D hierarchical superstructures

Hierarchical structures, in which structure is generated and controlled simultaneously at different size scales, have attracted increasing attention due to their potentials in both theoretical research and practical applications. In this review, a "non-classical crystallization" mechanism is discussed for their possibilities in morphology control of hierarchically-structured materials. Differently, this crystallization route is not based on the attaching and detaching of monomers as happened in the classical case, but through the self-organization of preformed building blocks as nanosized subunits, whose oriented attachment leads to mesocrystals with favorable morphology and texture. Representative materials including both inorganic and organic crystals are reported with possible mechanisms proposed. Synthetic protocols based on this mechanism provide unique inspirations for materials design and could be applied to morphological and structural control of new materials with optimized functions.

Mesocrystalline TiO_(2) nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystaUine anatase TiO_(2) nanosheets with highly exposed{001}facets was developed through topotactic transformation.Unique mesocrystalline{001}-faceted TiO_(2) nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the{001}-faceted TiO_(2) nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed{001}facets,in addition to the advantageous features of low-dimensional structure arrays(e.g.,fast electron transport and efficient charge collection),the obtained TiO_(2) nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells(DSSCs).Particularly,{001}-faceted TiO_(2) nanosheet arrays-15μm long annealed at 500℃showed a power conversion efficiency of 7.51%.Furthermore,a remarkable efficiency of 8.85%was achieved for a DSSC based on doubleqayered TiO_(2) nanosheet arrays-35μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.

Kinetics-controlled growth SnO2 nanorod arrays for superior rate performance of aligned mesocrystalline lithium-ion batteries with

A general method for facile kinetics-controlled growth of aligned arrays of mesocrystalline SnO2 nanorods on arbitrary substrates has been developed by adjusting supersaturation in a unique ternary solvent system comprising acetic acid, ethanol and water. The hydrolysis processes of Sn（IV） as well as the nucleation and growth of SnO2 crystals were carefully controlled in the mixed solvents, leading to an exclusively heterogeneous nucleation on a substrate and the subsequent growth into mesocrystalline nanorod arrays. In particular, aligned arrays of hierarchically structured, [001]-oriented mesocrystalline SnO2 nanorods with four {110} lateral facets can be readily grown on Ti foil as well as many other inert substrates such as fluoride-doped tin oxide （FTO）, Si, graphite, and polytetrafluoroethylene （Teflon）. Due to the unique combination of the mesocrystalline structure and the one-dimensional nanoarray structure, the obtained mesocrystalline SnO2 nanorod arrays grown on metallic Ti substrate exhibited an excellent rate performance with a high initial Coulombic efficiency of 65.6% and a reversible capacity of 720 mA.h/g at a charge/discharge rate of 10 C （namely, 7,820 mA/g） when used as an anode material for lithium-ion batteries.

Metallic mesocrystal nanosheets of vanadium nitride for high-performance all-solid-state pseudocapacitors

Transition metal nitrides （TMNs） are of particular interest by virtue of their synergic advantages of superior electrical conductivity, excellent environmental durability and high reaction selectivity, yet it is difficult to achieve flexible design and operation. Herein, mesocrystal nanosheets （MCNSs） of vanadium nitride （VN） are synthesized via a confined-growth route from thermally stable layered vanadium bronze, representing the first two-dimensional （2D） metallic mesocrystal in inorganic compounds. Benefiting from their single-crystalline-like long-range electronic connectivity, VN MCNSs deliver an electrical conductivity of 1.44×10^5 S/m at room temperature, among the highest values observed for 2D nanosheets. Coupled with their unique pseudocapacitance, VN MCNS-based flexible supercapacitors afford a superior volumetric capacitance of 1,937 mF/cm3. Nitride MCNSs should have wide applications in the energy storage and conversion fields because their intrinsic high conductivity is coupled with the reactivity of inorganic lattices.

Mesocrystalline TiO2/sepiolite composites for the effective degradation of methyl orange and methylene blue

Mesocrystalline TiO2/sepiolite （TiS） composites with the function of adsorption and degradation of liquid organic pollutants were successfully fabricated via a facile and low-cost solvothermal reaction. The prepared TiS composites were characterized by FESEM, HRTEM, XRD, XPS, N2 adsorption-desorption, UV-vis DRS, and EPR. Results revealed the homogeneous dispersion of highly reactive TiO2 mesocrystals on the sepiolite nanofibers. Thereinto each single-crystal-like TiO2 mesocrystal comprised many [001]-oriented anatase nanoparticles about 10-20 nm in diameter. The photocatalytic activity was further evaluated by the degradation of anionic dye （methyl orange） and cationic dye （methylene blue） under the UV-vis light （350≤λ≤780 nm） irradiation. By selecting appropriate experimental conditions, we can easily manipulate the photocatalytic performance of TiS composites. The optimal TiS catalyst （the sepiolite content of 28.5 wt.%, and the reaction time of 24 h） could efficiently degrade methyl orange to 90.7% after 70 min, or methylene blue to 97.8% after 50 min, under UV-vis light irradiation. These results can be attributed to their synergistic effect of high crystallinity, large specific surface area, abundant hydroxyl radicals, and effective photogenerated charge separation.

A general bottom-up synthesis of CuO-based trimetallic oxide mesocrystal superstructures for efficient catalytic production of trichlorosilane

Mesocrystals, the non-classical crystals with highly ordered nanoparticle superstructures, have shown great potential in many applications because of their newly collective properties. However, there is still a lack of a facile and general synthesis strategy to organize and integrate distinct components into complex mesocrystals, and of reported application for them in industrial catalytic reactions. Herein we report a general bottom-up synthesis of CuO-based trimetallic oxide mesocrystals (denoted as CuO-M1Ox-M2Oy, where M1 and M2 = Zn, In, Fe, Ni, Mn, and Co) using a simple precipitation method followed by a hydrothermal treatment and a topotactic transformation via calcination. When these mesocrystals were used as the catalyst to produce trichlorosilane (TCS) via Si hydrochlorination reaction, they exhibited excellent catalytic performance with much increased Si conversion and TCS selectivity. In particular, the TCS yield was increased 19-fold than that of the catalyst-free process. The latter is the current industrial process. The efficiently catalytic property of these mesocrystals is attributed to the formation of well-defined nanoscale heterointerfaces that can effectively facilitate the charge transfer, and the generation of the compressive and tensile strain on CuO near the interfaces among different metal oxides. The synthetic approach developed here could be applicable to fabricate versatile complicated metal oxide mesocrystals as novel catalysts for various industrial chemical reactions.