Reversible Color Research Articles

A Wide‐Temperature Adaptive Electrochromic Device Based on a Poly(vinyl alcohol)/Poly(acrylic acid) Gel Electrolyte

AbstractAs a promising energy‐saving technology, electrochromic technology has been widely investigated for practical applications. However, there is relatively few research about the applications under certain extreme climatic conditions since gel electrolytes often occur freezing and volatilizing. In this work, a poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) gel electrolyte with good anti‐freezing and heat‐resistance performance is developed. Utilizing hydrated tungsten oxide (WO3·xH2O) and polyaniline (PANI) as electrochromic materials and the PVA/PAA gel as electrolyte, a WO3·xH2O/PVA/PAA‐ethylene glycol (EG)‐H2O/PANI electrochromic device (WO3·xH2O/PAEH/PANI ECD) is obtained, which can work efficiently at wide operating temperatures from −20 to 60 °C. The device has multiple reversible color changes, a large optical modulation of 66.2% at 600 nm, high coloration efficiency of 386.0 cm2 C−1, fast responses (with coloration/bleaching times of 1.3/1.1 s), as well as excellent cyclic stability (82.0% of the initial optical modulation is still retained after 2100 cycles). This work reveals the potential application prospects of PAEH gel electrolyte in practical extreme operating conditions.

3D Micropatterning With Thermochromic Polymer Microfiber

AbstractAlthough 3D micropattern has received considerable attention due to their remarkable usability, the introduction of specific functions, such as “chromism”, is still a challenge mainly due to the lack of adequate functional materials that can be introduced into 3D printing system. In this study, 3D micropatterns with temperature‐responsive properties are created by elaborately aligned thermochromic polymer microfibers using charge reversal electro‐jet writing (CREW) method with a 3D printer. A reversible color change in response to the temperature change is exhibited in the micropattern, displaying various chromic colors, such as red, blue, and black, at their own thermochromic temperatures. Multiple‐color phases can be sequentially expressed in a single structure by incorporating pigments of different colors with distinguishable color shift ranges. Various patterning methods are proposed for manufacturing diverse patterns and demonstrating applications using combinations of color. In addition to directly increasing temperature, the thermochromic process of micropatterns can be induced by heat generated from external factors using electrical energy. These 3D thermochromic micropatterns using the CREW method can be extended to various fields, including sensors, clothing, and anti‐counterfeiting.

Structural Design of Hybrid Manganese(II) Halides for High Quantum Efficiency and Specific Response to Methanol.

Manganese(II) halides have been a new generation of optoelectronic materials due to their fascinating luminescent properties, however, lacking specific solvent-responsive analogues with high quantum efficiency. Herein, we prepared three single crystals, [Pr(MIm)2][MnBr4] ([Pr(MIm)2]2+ = 1,3-di(methylimidazolium)-propane, Compound 1), [Pr(EIm)2][MnBr4] ([Pr(EIm)2]2+ = 1,3-di(ethylimidazolium)-propane, Compound 2), and [Bu(MIm)2][MnBr4] ([Bu(MIm)2]2+ = 1,4-di(methylimidazolium)-butane, Compound 3), where different Bola-type cations were chosen as organic components to separate [MnBr4]2- tetrahedrons. All three compounds emitted bright green light with excellent quantum yields of 95.3, 80.0, and 96.2%, benefiting from the large Mn···Mn distance. More interestingly, Compound 3 showed a highly selective response to methanol in a series of tested organic solvents, with a rapid and reversible change in emission color from green to red. The single crystal of [Bu(MIm)2][MnBr4]·CH3OH with red emission proved that the luminescence switching was attributed to the adsorption of CH3OH molecules into the lattice space in the form of the O-H···Br hydrogen bonds. To our knowledge, for tetrahedrally coordinated Mn(II) species, the reversible emission color switching between green and red triggered by a solvent without the change of coordination number is achieved for the first time, providing promising applications for the specific detection of methanol.

Constructing Bionic Perovskite Smart Photovoltaic Windows with Switchable Colors and High Cycling Stability.

Smart photovoltaic windows (SPWs) provide a high-efficiency and energy-saving strategy owing to the dual capabilities of electricity generation and sunlight modulation achieved by tunable colors and transmittances. Due to the deterioration of chromic process on photovoltaic layers, SPWs usually suffer from poor cycling stability. Moreover, thermochromic SPWs with a multilayer structure usually change transmittance without reversible color transitions. To address these issues, inspired by chameleon skin, bionic SPWs are designed and constructed by integrating hydrogel, CsPbBr3 semitransparent perovskite solar cells (ST-PSCs), and transparent polymer film. The SPWs realize reversible transitions between transparent green (25°C) and opaque yellow (45°C) states in a short duration (2min) under natural conditions. By optimizing perovskite film and ultrathin-metal electrodes, CsPbBr3 ST-PSCs achieve a good trade-off between transmittance and efficiency, delivering the highest photovoltaic efficiency (8.35%) and a record light utilization efficiency (4.43). Ultimately, the multilayer SPWs maintain stable optical properties and more than 88% initial conversion efficiency after 100 transition cycles, presenting excellent cycling stability. This study proposes a novel approach and device structure for SPWs with high cycling stability, switchable colors, and switchable transmittances. It also paves the way for smart photovoltaic deployment in buildings and many other fields.

Reversible Color Loss in Aqueous Methyl Orange Solutions Induced by Freezing

Reversible Color Loss in Aqueous Methyl Orange Solutions Induced by Freezing

Electrochromic Covalent Organic Framework-Assembled Nanofibrous Membranes with Mimetic Chameleon Skin Architectures for Visible and Near-Infrared Camouflage Stealth.

The developments of modern surveillance technology pose great challenges to combat concealment for warfighters. Traditional camouflage suits cannot accommodate the need for camouflage stealth in complex warfare scenarios. Herein, a bidirectional diffusion-controlled in situ synthesis methodology is reported to achieve electrochromic nanofibrous membranes with mimetic chameleon skin structures (CSENs) by assembling electrochromic covalent organic frameworks on nanofibers. CSENs exhibit reversible color changes in the visible and near-infrared ranges under an applied potential with fast response times (25.8 s/26.2 s). The macro- and mesoporous structures in CSENs favored the transportation of electrolyte ions, achieving excellent color difference and coloration efficiency of 35.58 and 1053.26 cm2/C, respectively. Importantly, CSENs feature unique properties of self-standing, breathability, and flexibility, which are attributed to the micrometer pores constructed by entangled nanofibers. As a proof-of-concept study, the CSEN-based flexible electrochromic suit exhibits a dynamic camouflage function in real environments, showing promising properties as smart textiles for dynamic camouflage stealth.

Fluorescence switching of triarylamine-based polyamides with pendant pyrene units and its application in electrochromic smart displays

The pyrene group was directly connected to the triarylamine (TAA) unit through a benzene bridge via the Suzuki reaction to successfully prepare the diamine monomer. A series of new polyamides (PAs) based on TAA units were prepared by polycondensation. The PAs exhibited good solution processability and high thermal stability with the char yield in excess of 53% at 800°C in air atmosphere. In solvents with different polarities, these PAs showed solvatochromic effect and large stokes shift. Strongly photoluminescent PAs have a sensitive stimulus response to explosive and hazardous gas, and its fluorescence is easily turned off by the addition of trinitrophenol (TNP) and hydrogen chloride (HCl). And achieve fluorescence switching between exposure to HCl and ammonia (NH3) gas. The PAs exhibited a reversible color response in the electrochemical oxidation process, with no significant degradation in current and transmittance after 200 cycles. The sandwich structure multicolor electrochromic device can achieve electrochromic performance applied by different voltages.

Robust, intelligent photochromic cotton fabrics with superamphiphobicity and expedient UV detection ability

Multifunctional photochromic cotton fabrics have enormous application potential in our daily lives, but still suffer from poor durability, slow coloration, tedious fabrication process, and short service life. The hydrophilic and polysaccharide characteristics of cotton fabrics make them vulnerable to bacteria adhesion and proliferation. Herein, intelligent photochromic cotton fabrics featured with durable superamphiphobicity are fabricated by in situ growth of ZIF-8 nanoparticles encapsulating spirooxazine (SP) photochromic dyes on the fabric surface, followed by low surface energy treatment using a fluorocarbon resin (FR) via a dip-coating method. The resultant SP@ZIF-8/FR cotton fabrics exhibit superamphiphobicity with contact angles of over 150° to both water and oils (surface tension ≥30 mN/m). When exposed to UV light, the fabric rapidly changes its color from white to blue within 10 s and fades in 2 min under visible room light. The developed SP@ZIF-8/FR coating is durable against numerous damages in daily usage, such as machine laundry, abrasion and UV irradiation, without losing photochromic and superamphiphobic properties. The high durability and excellent reversible color response allow the coated fabric to intuitively and quantitatively monitor outdoor UV intensity. Owing to the presence of ZIF-8, the treated fabrics also show excellent antibacterial property with antibacterial rates of over 99 % against both E. coli and S. aureus. The developed fabric coating can be engineered to visually assess the UV intensity in the outdoor environment.

Facile Synthesis of Soft Core-Shell Nanospheres for Constructing Multiresponsive Photonic Crystal Security Patterns.

Responsive photonic crystals (RPCs) presenting tunable structural colors under external stimuli are widely applied in the fields of dynamic displays, sensors, and anticounterfeiting. However, the development of multiresponsive photonic crystal (MRPC) films possessing versatile variable optical properties remains a significant challenge due to the tedious synthetic procedure of multifunctional building blocks and complex assembly processes, thereby constraining their extensive applications. In the present work, a series of soft nanospheres with a hydrophobic cores and responsive hydrophilic shells have been synthesized by a facile one-step surfactant-free emulsion polymerization method. The MRPC patterns were then prepared by depositing soft nanosphere emulsions onto the 3D-printed substrates with a topological structure followed by drying at room temperature. The shells of soft nanospheres deformed and fused with each other, resulting in the formation of transparent MRPC film patterns. The MRPC patterns exhibited brilliant structural color in a wet state but lost the color again after complete drying. Such a reversible structural color was ascribed to the change of the refractive index (RI) of the hydrophilic shell layers of nanospheres according to wetting/drying state shifting. Moreover, the on-demand designed MRPC patterns could rapidly respond to external stimuli of temperature, pH, and organic solvents in a reversible manner, and multichannel encrypted security labels were also demonstrated. We postulate that our facile and feasible approach can be applied to the systematic design and large-scale production of MRPC patterns for a variety of applications.

Reversible Emission Color, Brightness, and Shape Changes of AIEgen‐containing Bulk Polymers

AbstractBulk polymers generally exhibit faster response, higher shape‐deformation speed, and stronger mechanical properties than the hydrogels. However, it still remains a formidable challenge to enable bulk polymers to exhibit reversible changes in shape and fluorescence simultaneously. Herein, for the first time, the temperature‐responsive reversible changes in fluorescence color, brightness, and shape of semi‐crystalline poly(ε‐caprolactone) (PCL) network doped with a D‐A based aggregation‐induced emission luminogen (AIEgen) is realized. The fabricated flower‐like and dragonfly‐shaped actuators show reversible blooming‐closing and wing fanning behaviors, respectively, as well as reversible fluorescence‐changing effects. Notably, the response and shape‐deformation speed as well as mechanical properties of the system is much better than the reported hydrogels. Moreover, a smart switch is developed to demonstrate the potential applications. The stick fabricated by the sample can lift and release an object 1000 times larger than its weight, serving as a color‐changing artificial muscle. This material design strategy may shine light on the design and preparation of other reversible shape‐deformation polymers in combination with stimuli‐responsive luminescence‐changing AIEgens, such as mechanochromic, thermochromic, and photochromic luminogens.

A 20‐Year Review of Inorganic Photochromic Materials: Design Consideration, Synthesis Methods, Classifications, Optical Properties, Mechanism Models, and Emerging Applications

AbstractInorganic photochromic materials (i.e., in‐PCMs) are developed as a research hot point in the lighting field due to their excellent optical characteristics, impressive body color modulation, etc. The aim of this work is to make a review on the developments of multi‐metals in‐PCMs (i.e., min‐PCMs) in the past 20 years. The review is structured based on the reversible coloration, crystal hosts, doped ions, PC properties, and mechanism of min‐PCMs and their applications. The synthesis methods of min‐PCMs are reviewed first and then the min‐PCMs are classified according to the types of the doped ions (i.e., single rare‐earth (i.e., RE) ion, multi RE ions, non‐RE ions, and/or the coupled arrangement of these ions). Meanwhile, the min‐PCMs co‐doped with RE and non‐RE ions, together with RE‐ and/or non‐RE‐doped and co‐doped dual crystal matrix, are also disclosed. In the 4th section, we underline the PC mechanisms and show the perspectives on how to produce the PC and obtain the related min‐PCMs. After that, diverse emerging applications of min‐PCMs are summarized, which include optical storage, anti‐counterfeiting, bio‐imaging, light detection, temperature sensing, photocatalysis, and smart windows. In the end, we conclude this review and forecast the promising opportunities and potential challenges of min‐PCMs in the future.

Development of biochromic paper strips from cellulose nanocrystals and anthocyanin extract from pomegranate (Punica granatum L.) for colorimetric determination of urea

AbstractAn anthocyanin (ACN) spectroscopic probe was extracted and immobilized into a matrix of cellulose nanocrystals (CNC)/urease enzyme to create a colorimetric nanocomposite film sensor. The ACN@CNC composite is a disposable molecular biosensor that uses urease as a catalyst, ACN as a molecular probe, and CNC as a probe carrier with a high surface area. The ACN spectroscopic probe was isolated from the pomegranate peel (Punica granatum L.). A mordant was applied to fix ACN onto CNC by forming nanoparticles (6–14 nm) of mordant/ACN (M/ACN) complexation. CNC showed diameters in the range of 11–21 nm, and crystal lengths of 55–130 nm. Under acid/base conditions, the ACN probe solution in distilled water exhibited a reversible color change, as shown by the UV–Vis absorption spectra. In order to create a biocomposite film, CNC were reinforced with a sodium alginate biopolymer. Upon exposure to urea in an aqueous solution, the ACN@CNC film biosensor changes color from purple (598 nm) to white (432 nm). The detection limit of urea was determined at 25–450 ppm. Various methods were utilized to investigate the morphological properties of CNC and ACN@CNC films.

Bioinspired Polydopamine Modification for Interface Compatibility of PDMS-Based Responsive Structurally Colored Textiles.

Textiles that can repeatedly change color in the presence of external stimuli have attracted great interest. Effectively designing to produce such functional textiles is essential, yet there remain challenges like producing stable coloration, rapid response, and reverse color changing. Here, the preparation of a magnetic field response (MFR) textile with a fast magnetic field response, brilliant structural coloration, and mechanical robustness is reported. The MFR textile is knitted by incorporating magnetic particles' ethylene glycol (EG) suspension within polydimethylsiloxane (PDMS)-based fibers. A surface modification strategy is designed to prevent EG from seeping out along the PDMS polymer chains. A PDMS fiber is encapsulated in waterborne polyurethane, and a polydopamine joint layer is used. The MFR textile demonstrates magnetic field-triggered structural colors, and the breaking strength and elongation at break of each composite fiber are improved. In addition, multishaped patterns can be printed on the MFR textile with the help of the photo etching technology, which enhances the applications of the new functional textiles.

Rapid-response nanofiber films against ammonia based on black wolfberry anthocyanins, polyvinyl alcohol and sodium alginate for intelligent packaging

To develop novel intelligent indicator films, the mixture of anthocyanin (BWA), polyvinyl alcohol (PVA) and sodium alginate (SA) were spun into PVA/SA/BWA nanofiber films with BWA concentration of 0 %, 5 %, 10 %, and 15 % (based on PVA and SA) via electrospinning technology. The results showed that the BWA was sensitive to pH and was controlled release from films. With increasing BWA concentration, the fiber diameter, tensile strength, and elongation at break gradually decreased, while water contact angle, thickness, moisture content, and antioxidant properties gradually increased. The electrospinning films exhibited high sensitivity to ammonia with rapid color changes in 1 s and excellent color reversibility and color stability within 21 d. The application for shrimp packaging showed that the colorimetric response of the films was closely related to the changes in pH, total volatile basic nitrogen (TVB-N), and total viable count (TVC) of shrimp. This suggests that the prepared films are promising in application for intelligent packaging.

Methyl- and fluoro-substituted triphenylamine core toward fast-switching visible and near-infrared electrochromic polymers

Herein, two monomers MTPA and FTPA, and their corresponding polymers (PMTPA and PFTPA) based on a methyl-and fluoro-substituted triphenylamine were synthesized by Stille reaction and electropolymerization. MTPA exhibited the red-shift absorption and fluorescence emission spectra, and lower Eonset (0.53 V) compared with FTPA (0.57 V), which is beneficial to achieve high-quality polymers. The polymer films exhibited reversible color transition from yellow green to deep blue for PMPTA and from dark brown to light blue for PFTPA, respectively. In addition, both PMTPA and PFTPA films exhibited good optical contrasts of 36 % and 40 % at 1100 nm, respectively. The coloration efficiency and response times at 1100 nm are 196.4 C−1 cm2 with 0.6 s for PMTPA, and 160.9 C−1 cm2 with 1.4 s for PFTPA, respectively. These polymer films demonstrated excellent electrochemical property and electrochromic performance. These results will also provide a new strategy to rationally design the excellent electrochromic polymers based on the triphenylamine core.

Co-Complexes-Based Self-Oscillating Gels Driven by the Belousov-Zhabotinsky Reaction.

We report the synthesis of novel cobalt complexes-based catalysts designed for the oscillatory Belousov-Zhabotinsky (BZ) reaction. For the first time, we introduce cobalt complex-based self-oscillating gels that demonstrate autonomous color oscillations within a BZ reagent solution, functioning without the need for any external stimuli. We created acrylamide-based self-oscillating gels containing immobilized tris(2,2'-bipyridine)cobalt(II) or tris(1,10-phenanthroline)cobalt(II) complexes and gels containing covalently bound (5-acrylamido-1,10-phenanthroline)bis(2,2'-bipyridine)cobalt(II), (5-acrylamido-1,10-phenanthroline)bis(1,10-phenanthroline) cobalt(II), or tris(5-acrylamido-1,10-phenanthroline)cobalt(II) complexes. When the BZ reaction takes place within the gels, it results in the observation of moving chemical waves and reversible color changes. We believe that Co-complexes-based self-oscillating gels have potential applications in the design of soft actuators and chemical devices for signal processing.

Reversible Modulation of Plasmonic Coupling of Gold Nanoparticles Confined within Swellable Polymer Colloidal Spheres.

Dynamic optical modulation in response to stimuli provides exciting opportunities for designing novel sensing, actuating, and authentication devices. Here, we demonstrate that the reversible swelling and deswelling of crosslinked polymer colloidal spheres in response to pH and temperature changes can be utilized to drive the assembly and disassembly of the embedded gold nanoparticles (AuNPs), inducing their plasmonic coupling and decoupling and, correspondingly, color changes. The multi-responsive colloids are created by depositing a monolayer of AuNPs on the surface of resorcinol-formaldehyde (RF) nanospheres, then overcoating them with an additional RF layer, followed by a seeded growth process to enlarge the AuNPs and reduce their interparticle separation to induce significant plasmonic coupling. This configuration facilitates dynamic modulation of plasmonic coupling through the reversible swelling/deswelling of the polymer spheres in response to pH and temperature changes. The rapid and repeatable transitions between coupled and decoupled plasmonic states of AuNPs enable reversible color switching when the polymer spheres are in colloidal form or embedded in hydrogel substrates. Furthermore, leveraging the photothermal effect and stimuli-responsive plasmonic coupling of the embedded AuNPs enables the construction of hybrid hydrogel films featuring switchable anticounterfeiting patterns, showcasing the versatility and potential of this multi-stimuli-responsive plasmonic system.

Synthesis, structure, and photochromic properties of Zn-coordination polymers derived from hexyl viologen cations

This study presents the synthesis, structural characterization, and investigation of the photochromic properties of two Zn-coordination polymers, formulated as {(HV)0.5[Zn(MIC)(HMIC)]·H2O}n (1) and {(HV)2[Zn4(BTEC)3]}n (2) (H2MIC = 5-methylisophthalic acid, H4BTEC = 1,2,4,5-benzenetetracarboxylic acid, HVBr2 = 1,1′-bis(n-hexyl)-4,4′-bipyridinium dibromide), derived from hexyl viologen cations. Compound 1 is characterized by a one-dimensional (1D) structure, while compound 2 exhibits a three-dimensional (3D) architecture, both crystallizing in distinct space groups and showcasing unique assembly and composition. Detailed structural analysis reveals the coordination modes of Zn(II) ions within these polymers. The photochromic behavior of two compounds under UV light exposure was thoroughly examined through ultraviolet-visible (UV–vis) and electron paramagnetic resonance (EPR) spectroscopy, demonstrating reversible color changes from light yellow to blue upon irradiation, with distinct rates of decolorization indicative of the stability of photo-induced viologen radicals. This reversibility was successfully replicated over multiple cycles, underscoring the durability of the photochromic transition. Furthermore, powder X-ray diffraction (PXRD) data confirmed the maintenance of crystal structures throughout the photochromic process, dismissing photolysis or photo-induced isomerization as underlying mechanisms. Instead, the observed photochromism is attributed to efficient electron transfer facilitated by the proximity between electron-donating and electron-withdrawing groups within the coordination polymers. This study highlights the influence of structural parameters on the photochromic properties of viologen-based coordination polymers, offering insights into the design of photo-responsive materials.

Ionic conductivity and dielectric characteristics of a Li incorporated PVA electrolyte membrane and a study of a fully solid-state electrochromic device based on it

The construction and study of a fully solid state electrochromic (EC) device with cathodic coloration exhibiting very fast response times (< 1s) is reported using a WO3 EC layer and a poly (vinyl alcohol) (PVA)- Lithium acetate membrane electrolyte. Broadband dielectric studies on the polymer membranes with different Li concentrations show multiple relaxation mechanisms out of which a segmental relaxation prominent beyond a certain composition is strongly correlated with Li-ion conduction yielding better ionic conductivity and reversible coloration in the EC device. The relatively high Li conductivity in PVA has a direct correspondence with the lowering of the crystallinity of PVA and a decrease of the glass transition temperature, Tg with increasing Li addition. A simple model of the coloration process suggests that the short electrolyte diffusion length coupled with a high electric field and an interfacial emf that varies as ≈t−0.6 results in the swift current response of the film with an optimal performance at 20 wt.% Li in PVA, exceeding which irreversible coloration can occur on the surface. The transient current is crucial for the observed swift switching characteristics. Ageing studies for almost a month indicate potential stability of the EC device for over 150 cycles.

Easy Processable Photomechanical Thin Film Involving a Photochromic Diarylethene and a Thermoplastic Elastomer in Supramolecular Interaction.

A novel supramolecular photoactuator in the form of a thin film of centimetric size has been developed as an alternative to traditional liquid crystal elastomers (LCE) involving azobenzene (AZO) units or photochromic microcrystals. This thin film is produced through spin coating without the need for alignment or crosslinking. The photoactuator combines a photochromic dithienylethene (DTE) functionalized with ureidopyrimidinone (UPy) units, and a telechelic thermoplastic elastomer, also functionalized with UPy, allowing quadruple hydrogen bonding between the two components. Upon alternating ultraviolet (UV) and visible light exposure, the film exhibits reversible bending and color changes, studied using displacement and absorption tracking setups. For the first time, the photomechanical effect (PME) is quantitatively correlated with photochromism, showing that DTE units drive the movement under both UV (photocyclization) and visible (photoreversion) light. In situ illumination techniques reveal that the PME arises from photoinduced strain within 160 nm UPy-bonded DTE domains, which expand and contract by approximately 50% under UV and visible light, respectively. The semicrystalline nature of the elastomer and a robust supramolecular network connecting both components are critical in converting microscopic photostrain into macroscopic actuation.