Fabrication of BaTiO_3 Inverse Opal Photonic Crystal

The colloidal crystal template or opal with a closed-packed face centered cubic (fcc) lattice, was prepared from monodisperse polystyrene (PS) spheres by gravity sedimentation. The template was used for the generation of photonic crystal. The template provided void space for infiltration of liquid precursor composed of titanium butyloxide, barium acetate, ethanol, and acetic acid. The opal composite was hydrolyzed, dried, sintered by heating for completely removing PS spheres to form BaTiO3 photonic crystals with inverse opal structure. The PS spheres were replaced by air spheres, which interconnected each other through the windows on the BaTiO3 wall. So both the BaTiO3 wall and air void constitute continuous phases.

PAM-PAA microgel inverse opal photonic crystal and pH response

The colloidal crystal template or opal with a closed-packed face-centered cubic （fcc） lattice was prepared from monodisperse polystyrene （PS） spheres by vertical sedimentation. The template provided void space for infiltration of monomer precursor composed of acrylate acid, acrylamide and ammonium-persulfate, as well as microgel from the subsequent copolymerization. The sample was immersed in dimethylbenzene for completely removing PS spheres to form PAM inverse opal hydrogels （IOHPAM） or PAM/PAA inverse opal hydrogels （IOHPAM/PAA） photonic crystals. The PS spheres were replaced by air spheres, which interconnected each other through the windows. The study of responses to pH show that there are two peaks for both IOHPAM and IOHPAM/PAA films, but the IOHPAM/PAA peaks shift to higher pH, and the peaks are independent with the AA content.

Hierarchically Inverse Opal Porous Scaffolds from Droplet Microfluidics for Biomimetic 3D Cell Co-Culture

With the advantages of better mimicking the specificity of natural tissues,three-dimensional(3D)cell culture plays a major role in drug development,toxicity testing,and tissue engineering.However,existing scaffolds or microcarriers for 3D cell culture are often limited in size and show suboptimal performance in simulating the vascular complexes of living organisms.Therefore,we present a novel hierarchically inverse opal porous scaffold made via a simple microfluidic approach for promoting 3D cell co-culture techniques.The designed scaffold is constructed using a combined concept involving an emulsion droplet template and inert polymer polymerization.This work demonstrates that the resultant scaffolds ensure a sufficient supply of nutrients during cell culture,so as to achieve large-volume cell culture.In addition,by serially planting different cells in the scaffold,a 3D co-culture system of endothelial-cellencapsulated hepatocytes can be developed for constructing certain functional tissues.It is also demonstrated that the use of the proposed scaffold for a co-culture system helps hepatocytes to maintain specific in vivo functions.These hierarchically inverse opal scaffolds lay the foundation for 3D cell culture and even the construction of biomimetic tissues.

Thermal-responsive Photonic Crystals based on Physically Cross-linked Inverse Opal Nanocomposite Hydrogels

A thermal-responsive photonic crystal material was fabricated by forming an inverse opal nanocomposite hydrogel of poly(N-isopropylacrylamide)(IONHPNIPAm)within the interstitial space of a polystyrene photonic crystal template.In IONHPNIPAm,PNIPAm were physically cross-linked with two kinds of nanoparticles(carbon dots and laponite clays).The integration of carbon dots and laponite clays for physical crosslinking endowed IONHPNIPAm sufficient strength and self-healing property.IONHPNIPAm films can be completely peeled from the substrates to be utilized as an independent photonic crystal material.The structural color and optical diffraction of the IONHPNIPAm exhibits a rapid reversible change in response to external thermal stimuli due to its physical cross-linking feature.Moreover,the IONHPNIPAm shows clear fluorescence due to the introduction of carbon dots,which enables a convenient way for chemical detection(such as the detection of silver ions).This stimuli-responsive photonic crystal materials based on physically cross-linked inverse opal nanocomposite hydrogels with fast response and good mechanical stability are promising for applications in the fields of smart optical detectors,thermal-responsive sensors and chemical detectors.

Controlling the photoluminescence spectroscopy of quinacrine dihydrochloride by SiO_2 inverse opal photonic crystal

Manipulation of the photoluminescence spectra of light-emitting materials doped in three-dimensional （3D） inverse opal photonic crystals is investigated. Quinacrine dihydrochloride molecules doped highly ordered SiO2 inverse opal is successfully synthesized by co-assembly combined with double-substrate vertical infiltrate method. The quinacrine dihydrochloride-doped and-undoped SiO2 inverse opals each exhibit an apparent photonic band gap （PBG） in the visible light region. Significant suppression of the emission is observed when the PBG is overlapped with the quinacrine dihydrochloride emission bands. The mechanism of suppression effect of PBG in inverse opal on the fluorescence intensity of quinacrine dihydrochloride molecules is studied.

Design and mechanism insight on SiC quantum dots sensitized inverse opal TiO_(2) with superior photocatalytic activities under sunlight

The combination of SiC quantum dots sensitized inverse opal TiO_(2) photocatalyst is designed in this work and then applied in wastewater purification under simulated sunlight.From various spectroscopic techniques,it is found that electrons transfer directionally from SiC quantum dots to inverse opal TiO_(2),and the energy difference between their conduction/valence bands can reduce the recombination rate of photogenerated carriers and provide a pathway with low interfacial resistance for charge transfer inside the composite.As a result,a typical type-II mechanism is proved to dominate the photoinduced charge transfer process.Meanwhile,the composite achieves excellent photocatalytic performances(the highest apparent kinetic constant of 0.037 min^(-1)),which is 6.2 times(0.006 min^(-1))and 2.1 times(0.018 min^(-1))of the bare inverse opal TiO_(2) and commercial P25 photocatalysts.Therefore,the stability and non-toxicity of SiC quantum dots sensitized inverse opal TiO_(2) composite enables it with great potential in practical photocatalytic applications.

Conductive PS inverse opals for regulating proliferation and differentiation of neural stem cells

The development of neural tissue engineering has brought new hope to the treatment of spinal cord injury(SCI).Up to date,various scaffolds have been developed to induce the oriented growth and arrangement of nerves to facilitate the repair after injury.In this work,a conductive and anisotropic inverse opal substrate was presented by modifying polystyrene(PS)inverse opal films with carbon nanotubes and then stretching them to varying degrees.The film had good biocompatibility,and neural stem cells(NSCs)grown on the film displayed good orientation along the stretching direction.In addition,benefiting from the conductivity and anisotropy of the film,NSCs differentiated into neurons significantly.These results suggest that the conductive and anisotropic PS inverse opal substrates possess value in nerve tissue engineering regeneration.

Single-material Solvent-sensitive Fluorescent Actuator from Carbon Dots Inverse Opals Based on Gradient Dewetting

A novel solvent-sensitive fluorescent actuator with reversibility has been obtained from carbon dots （CDs） inverse opals, which is prepared via infiltrating CDs solution into the interstice of colloidal crystal template, thermal polymerization of CDs materials and removing the colloidal template. The as-prepared CDs inverse opal actuator shows a bending angle of 75° in 10.2 s, bending rate of 7.35 （°）.s-1. In particular, the fluorescence intensity of the films varies during the actuating process. The actuating behavior is attributed to the inhomogeneous swelling/shrinking of the film, which originates from the gradient dewetting by solvent evaporation and hydrogen-bonding interaction between the solvent molecules and oxygen/hydrogen ions of CDs side chain. The CDs inverse opal actuator has the advantages of quick response, good repeatability and strong fluorescence, which gives an important insight into the design and manufacture of novel and advanced solvent-actuators.

Delicate synthesis of quasi-inverse opal structural Na_(3)V_(2)(PO_(4))_(3)/N-C and Na4MnV(PO_(4))_(3)/N-C as cathode for high-rate sodium-ion batteries

Poor conductivity and sluggish Na^(+) diffusion kinetic are two major drawbacks for practical application of sodium super-ionic conductor(NASICON) in sodium-ion batteries. In this work, we report a simple approach to synthesize quasi-inverse opal structural NASICON/N-doped carbon for the first time by a delicate one-pot solution-freeze drying-calcination process, aiming at fostering the overall electrochemical performance. Especially, the quasi-inverse opal structural Na_(3)V_(2)(PO_(4))_(3)/N-C(Q-NVP/N-C) displayed continuous pores, which provides interconnected channels for electrolyte permeation and abundant contacting interfaces between electrolyte and materials, resulting in faster kinetics of redox reaction and higher proportion of capacitive behavior.As a cathode material for sodium-ion batteries, the Q-NVP/N-C exhibits high specific capacity of 115 mAh·g^(-1) at 1C, still 61 mAh·g^(-1) at ultra-high current density of 100C,and a specific capacity of 89.7mAh·g^(-1) after 2000 cycles at 20C.This work displays the general validity of preparation method for not only Q-NVP/N-C,but also Na_(3)V_(2)(PO_(4))_(3),which provides a prospect for delicate synthesis of NASICON materials with excellent electrochemical performance.

Fluorinated inverse opal carbon nitride combined with vanadium pentoxide as a Z-scheme photocatalyst with enhanced photocatalytic activity

In this work,Z-scheme V_(2)O_(5) loaded fluorinated inverse opal carbon nitride(IO F-CN/V_(2)O_(5)) was synthesized as a product of ternary collaborative modification with heterostructure construction,element doping and inverse opal structure.The catalyst presented the highest photocatalytic activity and rate constant for degradation of typical organic pollutants Rhodamine B(RhB)and was also used for the efficient removal of antibiotics,represented by norfloxacin(NOR),sulfadiazine(SD)and levofloxacin(LVX).Characterizations confirmed its increased specific surface area,narrowed bandgap,and enhanced visible light utilization capacity.Further mechanism study including band structure study and electron paramagnetic resonance(EPR)proved the successful construction of Z-scheme heterojunction,which improved photogenerated charge carrier migration and provide sufficient free radicals for the degradation process.The combination of different modifications contributed to the synergetic improvement of removal efficiency towards different organic pollutants.

Preparation and optical properties of tin dioxide inverse opal film

As a novel structure, inverse opal, with threedimensional periodic macropore and mesopore and huge specific surface area, has great promising applications. In this paper, tin dioxide (SnO_(2)) inverse opal films were prepared with sol–gel method by cooperative opal template. The surface morphologies of SnO_(2)inverse opal films were examined by scanning electron microscopy (SEM), the inner structure of SnO_(2)inverse opal films was examined by transmission electron microscopy (TEM), the optical properties of SnO_(2)inverse opal films were studied and discussed in detail. Optical reflectance spectra reveal that, for the opal films, the wavelengths of the reflectance peak confirmed by the experimental reflectance spectra are consistent with the theoretical values;for the SnO_(2)inverse opal films, the wavelengths of the reflectance peak confirmed by the experimental reflectance spectra deviate from theoretical values largely.

Upconversion luminescence and color tunable properties in Yb-Tb codoped Ca_(0.15)Zr_(0.85)O_(1.85) inverse opal

The upconversion （UC） luminescence and color tunable properties of Tb3＋ ions were investigated by steady spectral under 980 LD excitation in the Cao.15ZrO.8501.85：Yb,Tb inverse opals fabricated by the self-assembly technique in combination with a sol-gel method. The inhibition of UC emission was inspected if the Tb3＋ UC emission band was in the regions of the photonic bandgap, while enhancement of the UC emission occurred if the UC emission band located at the edge of the bandgap. Color modification of the UC emission was successfully obtained by the suppression or enhancement effect of the photonic band gap on the UC emission.

Investigation of the mechanism of upconversion luminescence in Er^(3+)/Yb^(3+) co-doped Bi_2Ti_2O_7 inverse opal

Three-dimensional-ordered Yb/Er co-doped Bi2Ti207 inverse opal, powder, and disordered reference sam- ples are prepared and their upconversion （UC） emission properties and mechanisms are investigated. Sig- nificant suppression of UC emission is detected when the photonic band-gaps overlap with Er3＋ UC green emission bands. Interestingly, green and red UC emissions follow a two-photon process in the powder sample but a three-photon one in the inverse opal.

Fluorescence Retention of Organosilane-polymerized Carbon Dots Inverse Opals in CuCl Suspension

A novel and fluorescence retention inverse opal has been achieved from organosilane-polymerized carbon dots（SiCDs）, which is prepared via infiltrating SiCD solution into the interstice of photonic crystal（PC） template, low temperature treatment, heating polymerization and removing the colloidal template. The as-prepared SiCD inverse opals demonstrate close-cell structure, which is completely different from conventional open-cell structure. Then the fluorescence signal of as-prepared sample keeps almost unchanged in CuCl suspension while the fluorescence of SiCD solution can be quenched by CuCl suspension through an effective electron transfer process. This phenomenon can be attributed to the combined effect of high hydrostatic pressure in the pore structure, stable crosslinking network and fluorescence enhancement by PC structure. The SiCD inverse opals have advantages of unique close-cell structure, easy preparation and good repeatability that give an important insight into the design and manufacture of novel and advanced optical devices.

In situ establishment of Co/MoS_(2) heterostructures onto inverse opal‐structured N,S‐doped carbon hollow nanospheres:Interfacial and architectural dual engineering for efficient hydrogen evolution reaction

Rational design of low‐cost and high‐efficiency non‐precious metal‐based catalysts toward the hydrogen evolution reaction(HER)is of paramount significance for the sustainable development of the hydrogen economy.Interfacial manipulationinduced electronic modulation represents a sophisticated strategy to enhance the intrinsic activity of a non‐precious electrocatalyst.Herein,we demonstrate the straightforward construction of Co/MoS_(2) hetero‐nanoparticles anchored on inverse opal‐structured N,S‐doped carbon hollow nanospheres with an ordered macroporous framework(denoted as Co/MoS_(2)@N,S-CHNSs hereafter)via a templateassisted method.Systematic experimental evidence and theoretical calculations reveal that the formation of Co/MoS_(2) heterojunctions can effectively modulate the electronic configuration of active sites and optimize the reaction pathways,remarkably boosting the intrinsic activity.Moreover,the inverse opal‐structured carbon substrate with an ordered porous framework is favorable to enlarge the accessible surface area and provide multidimensional mass transport channels,dramatically expediting the reaction kinetics.Thanks to the compositional synergy and structural superiority,the fabricated Co/MoS_(2)@N,S-CHNSs exhibit excellent HER activity with a low overpotential of 105mV to afford a current density of 10 mA/cm^(2).The rationale of interface manipulation and architectural design herein is anticipated to be inspirable for the future development of efficient and earth‐abundant electrocatalysts for a variety of energy conversion systems.

Intrinsic electrochemical activity of Ni in Ni_(3)Sn_(4) anode accommodating high capacity and mechanical stability for fast-charging lithium-ion batteries

Fast interfacial kinetics derived from bicontinuous three-dimensional(3D)architecture is a strategic feature for achieving fast-charging lithium-ion batteries(LIBs).One of the main reasons is its large active surface and short diffusion path.Yet,understanding of unusual electrochemical properties still remain great challenge due to its complexity.In this study,we proposed a nickel–tin compound(Ni_(3)Sn_(4))supported by 3D Nickel scaffolds as main frame because the Ni_(3)Sn_(4) clearly offers a higher reversible capacity and stable cycling performance than bare tin(Sn).In order to verify the role of Ni,atomic-scale simulation based on density functional theory systematically addressed to the reaction mechanism and structural evolution of Ni_(3)Sn_(4) during the lithiation process.Our findings are that Ni enables Ni_(3)Sn_(4) to possess higher mechanical stability in terms of reactive flow stress,subsequently lead to improve Li storage capability.This study elucidates an understanding of the lithiation mechanism of Ni_(3)Sn_(4) and provides a new perspective for the design of high-capacity and high-power 3D anodes for fast-charging LIBs.

MESO-STRUCTURED POLYMERIC HYDROGELS

Meso-structured (opal and inverse opal) polymeric hydrogels of varied morphology and composition wereprepared by using two methods: post-modification of the template-synthesized structured polymers and template-polymerization of functional monomers. A polyacrylic acid based inverse opal hydrogel was chosen to demonstrate its fastpH response by changing color, which is important in designing tunable photonic crystals. Template effects of the hydrogelson controlling structure of the template-synthesized inorganic materials were discussed. The catalytic effect of acid groups inthe templates was emphasized for a preferential formation of TiO_2 in the region containing acid groups, which allowedduplicating inorganic colloidal crytals from colloidal crystal hydrogels (or macroporous products from macroporoushydrogels) via one step duplication.

WO_(3) Inversce Opal Photonic Crystals: Unique Property, Synthetic Methods and Extensive Application

Tungsten trioxide inverse opal photonic crystals(WO_(3) IOPCs)not only possess the intrinsic properties of WO_(3)/but also own the unique characteristics of lOPCs structure.The evolution of preparation method of WO_(3) IOPCs has been briefly presented as electrodeposition method,sol-gel methodology and’dynamic hard-template’strategy in this review.Then the crystalline structure,optical property and electrical performance of WO_(3) IOPCs are later described.Afterwards,this review focuses on the wide application of WO_(3) lOPCs in chemical sensor,photo(electro)catalysis,electrochromic material and photochromic field in the last decade.Finally,a brief outlook over future investigation in preparation and modification,as well as promising application is proposed.This paper aims to encourage the attention and effort of researchers on WO_(3) IOPCs and other semiconductor materials with lOPCs structure.

A sustained-release microcarrier effectively prolongs and enhances the antibacterial activity of lysozyme

Bacterial infections have become a great threat to public health in recent years.A primary lysozyme is a natural antimicrobial protein;however,its widespread application is limited by its instability.Here,we present a poly(N-isopropylacrylamide)hydrogel inverse opal particle(PHIOP)as a microcarrier of lysozyme to prolong and enhance the efficiency against bacteria.This PHIOP-based lysozyme(PHIOP-Lys)formulation is temperature-responsive and exhibits long-term sustained release of lysozyme for up to 16 days.It shows a potent antibacterial effect toward both Escherichia coli and Staphylococcus aureus,which is even higher than that of free lysozyme in solution at the same concentration.PHIOPs-Lys were demonstrated to effectively inhibit bacterial infections and enhance wound healing in a full-thickness skin wound rat model.This study provides a novel pathway for prolonging the enzymatic activity and antibacterial effects of lysozyme.

Slow Photon-Enhanced Heterojunction Accelerates Photocatalytic Hydrogen Evolution Reaction to Unprecedented Rates

In photocatalysis,both the photogenerated charge separation and transport and the induced light utilization greatly influence performance.In this work,highly ordered CdS@ZnO core-shell inverse opal(CdS@ZnO-csIO)nanocomposites have been successfully designed as a model to couple the heterojunction system with the slow photon effect for photocatalytic H2 production.Theoretical calculations and experimentation provide direct evidence for the slow photon effect in the CdS@ZnO-csIO nanocomposites.The type II heterojunction is responsible for promoting the migration and separation of photogenerated charges,and the slow photon effect is in charge of enhancing light harvesting in the CdS@ZnO-csIO nanocomposites.This synergy of two functions gives rise to a significantly enhanced photocatalytic H2 production rate under simulated solar light for the CdS@ZnO-csIO nanocomposites.The highest H2 production rate reaches 48.7 mmol g^(−1)h^(−1)under simulated solar light with the benchmark performance for all reported CdS@ZnO composites.Our work provides proof-of-principle that coupling the heterojunction system with the slow photon effect can greatly enhance the photocatalytic activity of composite photocatalysts.