Blue Materials Research Articles

High-Entropy Prussian Blue Analogues as High-Capacity Cathode Material for Potassium Ion Batteries

Potassium ion batteries, due to their similar electrochemical principles to lithium-ion batteries and the abundance of metal sources, are considered one of the alternatives to lithium-ion batteries. The development of new cathode materials has always been a research focus in this field. Among them, Prussian blue materials, with their three-dimensional open and flexible metal framework structure, can efficiently and reversibly store potassium ions. However, Prussian blue cathode materials still face issues such as poor reversibility and low capacity, which limit their application scope. This study investigates the preparation of high-entropy Prussian blue analogues materials to enhance electrochemical performance. The doping of five different transition metals (Fe2⁺, Co2⁺, Cu2+, Ni2+, and Mn2+) sharing the same nitrogen coordination sites results in a configurational entropy greater than 1.5 R for the material. HEPB-1 cathode material (K1.75Mn0.26Fe0.01Ni0.01Cu0.08Co0.09 [Fe(CN)6]0.66·0.83H2O) shows better electrochemical performance, with the initial discharge capacity of 86.69 and 74.51 mAh g−1 (capacity retention is 75.2% after 100 cycles) at 20 and 100 mA g−1, respectively. The research results have provided new insights for the further development and application of potassium ion batteries.

Rational combination of Inverted-Pyramid structured Nickel-based Prussian blue with porous 3D carbon as high-performance sodium-ion batteries cathode

Metal based Prussian blue composite materials with heterogeneous structures possess substantial potential for enhancing both ionic and charge transfer processes, ultimately expediting electrochemical reaction kinetics for various battery devices. However, the limited bonding between carbon materials and Prussian blue analogues (PBAs) and the uncontrolled nucleation rate of metal component resulted in limited specific capacity and cyclic stability. Herein, we introduced a novel approach for the in-situ synthesis of Ni-PBA with an inverted-pyramid structure on a three-dimensional ultra-thin carbon frames (3DUC) substrate via a hydrothermal method. The inverted pyramid structure fits tightly with the 3DUC during nucleation to form a one-piece stable structure. This integration effectively curbs aggregation and hasty nucleation tendencies of NiPBA. Furthermore, the abundant voids and interconnected networks within the 3DUC structure significantly reduce ion diffusion path lengths, thereby lowering the Na diffusion barrier and enhancing the material’s capacitance contribution rate. Consequently, this cathode material exhibits commendable initial capacity (125.2 mAh/g at 50 mA g−1) and exceptional long-term cycling stability (with a capacity retention of 89.06 % after 900 cycles at 50 mA g−1). These findings hold significant promise for advancing the commercial viability of metal-PBA based electrodes by rational heterogeneous structure design.

Evaluation of the cumulative effect of photodynamic therapy and local fluoride on the microhardness and topography of demineralized enamel and cementum surfaces

BackgroundThe present study aimed to determine the cumulative effect of two photodynamic therapy methods with methylene blue and indocyanine green and two topical fluoride therapy methods with fluoride varnish and silver diamine fluoride alone and in combination on the microhardness and topography of demineralized enamel and cementum surfaces. Materials and methodsSeventy-two sound human teeth were selected, and their buccal and lingual surfaces were assigned to two main groups of enamel and cementum using simple randomization. The initial surface hardness (SH) of the enamel and cementum in each sample was determined using a micro-Vickers hardness tester using a 200-g force in 10 s. Then artificial caries was induced by immersion in a demineralizing/remineralizing solution (i.e., each tooth provided two samples, one on the buccal aspect and the other on the lingual aspect). Each enamel/cementum main group was divided into two subgroups using simple randomization based on the local fluoride type (fluoride varnish and silver diamine fluoride) and the type of the photosensitizer agent (methylene blue and indocyanine green). Finally, 16 groups were achieved (n = 9). The final surface hardness of the enamel and cementum samples was determined as described above. Finally, the sample surfaces were prepared for the surface topography evaluation under a scanning electron microscope. The baseline microhardness was compared between the 16 study groups in the first step using one-way ANOVA. Then, three-way ANOVA was used to evaluate the effect of fluoride, laser, and surface (enamel and cementum) on microhardness. ResultsAll the groups exhibited decreased microhardness due to the induction of artificial caries. In both main groups of enamel and cementum, the lowest decrease in microhardness was recorded with combined photodynamic therapy and methylene blue photosensitizer material and fluoride varnish (15.1 % for cementum and 16.7 % for enamel), and the highest decrease in microhardness was recorded in the methylene blue group (35.7 % for cementum and 34.9 % for enamel). ConclusionThe combination of photodynamic therapy with the photosensitizer substance methylene blue or indocyanine green together with fluoride varnish or silver diamine fluoride is effective on the remineralization of demineralized enamel and cementum. Although there is no difference between the combination of photodynamic therapy with fluoride varnish compared to fluoride varnish alone, both of these treatments are more effective than using photodynamic therapy alone.

Microwave-assisted synthesis of highly uniform Prussian Blue@Carbon cathode materials for sodium-ion batteries

Prussian blue (PB) and its analogues (PBAs) as cathode material for sodium-ion batteries suffer from poor cycling stability because of crystal defects and sluggish ion diffusion kinetics. Composite with carbon materials is an effective solution to alleviate this problem. However, this is typically achieved through simple physical mixing or encapsulation, which relies heavily on the compatibility between carbon and PB, often resulting in composites that are neither stable nor uniform. Herein, we have developed a facile strategy that utilizes microwave radiation to anchor PB onto the surface of polyvinylpyrrolidone (PVP) functionalized graphene oxide (GO-PVP) through stable, uniform covalent bonds via the amide groups in PVP, in order to obtain an excellent composite material with Prussian blue and carbon materials for sodium-ion batteries. The as-prepared composite materials exhibit lower content of crystallization water and higher crystal integrity, delivering a high initial specific capacity of 165.2 mAh g−1 at 1 C rate and maintaining a capacity of 120.1 mAh g−1 after 500 cycles. This composite approach offers novel insights into the creation of uniform and stable PB/carbon materials as the cathode of sodium-ion batteries.

Preparation of dispersible carbon nitride powder and fabrication of its thin films by wet-process

To establish a low-cost and environment-friendly method for producing blue fluorescent materials and their thin films, we investigated the conditions for synthesizing graphitic carbon nitride (g-C3N4) powder from urea and melamine. We found that urea can be used to synthesize g-C3N4 at lower annealing temperatures than melamine. The synthesized g-C3N4 powder showed good dispersibility in deionized water and methanol, and it was found that relatively uniform g-C3N4 thin films could be obtained by low-speed spin-coating, especially with highly volatile methanol dispersions. These results indicate that blue fluorescent thin films can be fabricated using a wet process at room temperature.

Ultralong Blue Organic Room‐Temperature Phosphorescence Promoted by Green Assembly

AbstractIn recent years, there is a growing interest in developing ultralong organic room‐temperature phosphorescence (ORTP) with lifetimes in the range of seconds. As one of the important three primary colors, ultralong blue ORTP is an indispensable core component in RTP regulation and application, however, the large Stokes shift characteristics pose certain challenges in developing ultralong blue ORTP. Here, a new family of blue phosphors are synthesized and ultralong blue ORTP are realized through crystal assembly in water and organic phase. Remarkably, compared to crystal materials obtained in organic phases, assembly materials obtained in water enabled long‐lived blue ORTP with lifetimes up to 2.3 s and phosphorescence quantum yield reached as high as 29.27%. In addition to the efficient and green assembly form, such dark blue ORTP materials possessed high thermal stability and flexible tunability. Moreover, the superiority of the selected assembly components is demonstrated by comparing them with polymer assembly and the proposed blue ORTP materials show great potential in an organic programmable information encryption/anti‐counterfeiting.

Exploring Efficient Blue TADF Materials with Ultrafast Bipolar Charge Transport for High‐Efficiency Thick‐Layer OLEDs (Adv. Funct. Mater. 30/2024)

Exploring Efficient Blue TADF Materials with Ultrafast Bipolar Charge Transport for High‐Efficiency Thick‐Layer OLEDs (Adv. Funct. Mater. 30/2024)

Toward Full‐Color Vision Restoration: Conjugated Polymers as Key Functional Materials in Artificial Retinal Prosthetics

AbstractFor the prosthetic retina, a device replacing dysfunctional cones and rods, with the ability to mimic the spectral response properties of these photoreceptors and provide electrical stimulation signals to activate residual visual pathways, can relay sufficient data to the brain for interpretation as color vision. Organic semiconductors including conjugated polymers with four different bandgaps providing wavelength‐specific electrical responses are ideal candidates for potential full‐color vision restoration. Here, conjugated polymer photocapacitor devices immersed in electrolyte are demonstrated to elicit a photovoltage measured by a Ag/AgCl electrode 100 microns from the device of ≈−40 mV for 15–39 µW mm−2 of incident light power density at three wavelengths: 405 nm for blue photoreceptor candidate material, 534 nm for green, 634 nm for red. Photoresponse is substantially improved by introducing polymer donor/acceptor molecules bulk heterojunctions. Devices with bulk heterojunction configurations achieved at least −70 mV for green candidates with the highest at −200 mV for red cone candidates. These findings highlight the potential for organic materials to bridge the gap toward natural vision restoration for retinal dystrophic conditions such as age‐related macular degeneration, Stargardt disease, or retinitis pigmentosa and contribute to the ongoing advancements in visual prosthetic devices.

Highly Efficient Blue Host Compound Based on an Anthracene Moiety for OLEDs

We designed and successfully synthesized a novel anthracene-based host material, 10-(4-(naphthalen-1-yl)phenyl)-9-(naphthalen-3-yl)anthracene (2-NaAn-1-PNa). The 2-NaAn-1-PNa exhibited a PL max at 440 nm in film state and demonstrated a wide band gap of 2.95 eV, indicating its suitability as a blue host material. In an OLED device using 2-NaAn-1-PNa as the host and 3Me-1Bu-TPPDA as the dopant, real blue emission was achieved with an electroluminescence maximum (ELmax) at 460 nm and Commission Internationale de L’Eclairage coordinates of (0.133, 0.141). The device exhibited excellent EL characteristics, with an external quantum efficiency of 8.3% and a current efficiency of 9.3 cd/A at 10 mA/cm2. Furthermore, the efficiency roll-off was limited to only 1.9% up to 4000 nits, demonstrating exceptional performance.

Stepwise Stiffening Chromophore Strategy Realizes a Series of Ultralong Blue Room-Temperature Phosphorescent Materials.

Ultralong room-temperature phosphorescent (URTP) materials have attracted wide attention in anti-counterfeiting, optoelectronic display, and bio-imaging due to their special optical properties. However, room-temperature blue phosphorescent materials are very scarce during applications because of the need to simultaneously populate and stabilize high-energy excited states. In this work, a stepwise stiffening chromophore strategy is proposed to suppress non-radiative jump by continuously reducing the internal spin of the chromophore, and successfully developing a series of blue phosphorescent materials. Phosphorescence lifetimes of more than 3 s are achieved, with the longest lifetime reaching 5.44 s and lasting more than 70 s in the naked eye. As far as is know, this is the best result that has been reported. By adjusting the chromophore conjugation, multicolor phosphorescences from cyan to green have been realized. In addition, these chromophores exhibit the same excellent optical properties in urea and polyvinyl alcohmance (PVA). Finally, these materials are successfully applied to luminescent displays.

Self-Sustained-Release Strategy Realizes Colloid Oriented Assembly to Fabricate Prussian Blue with Hierarchical Structure.

The controlled self-assembly of nanomaterials has been a great challenge in nanosynthesis, especially for hierarchical architectures with high complexity. Particularly, the structural design of Prussian blue (PB) series materials with robustness and fast nucleation is even more difficult. Herein, a self-sustained-release strategy based on the slow release of metal ions from coordination ions is proposed to guide the assembly of PB crystals. The key to this strategy is the slow release by ligand, which can create ultra-low concentrations of metal ions so as to provide the possibility to realize the surface charge manipulation of PB primary colloids. By adding electrolyte or changing the polarity of the solution, the surface charge regulation of PB colloid is realized, and the PB hierarchical structures with branch fractal structure (PB-BS), octahedral fractal structure, and spherical fractal structure are effectively constructed. This work not only achieves the designability of the PB structure, but also synchronizes the functionalization during the PB assembly growth process by in situ encapsulation of the effective catalytic active component L-Ascorbic acid. As a result, the assembled PB-BS exhibits greatly enhanced catalytic activity and selectivity in styrene oxidation with the selectivity of oxidized styrene increasing from 35.6% (PB) to 80.5% (PB-BS).

Blue fluorescent waterborne polyurethane‐based transition metal complexes with antibacterial activity

AbstractEfficient and stable blue fluorescent materials are the key components of light‐emitting devices and have received wide attention. Herein, transition metal complexes Zn(5‐AQ)2, Cu(5‐AQ)2, and Cd(5‐AQ)2 are prepared by using 5‐aminoquinoline (5‐AQ) as ligand and Zn2+, Cu2+, and Cd2+ as the central ions, respectively. Then, waterborne polyurethane (WPU)‐based transition metal complexes Zn(5‐AQ)2‐WPU, Cu(5‐AQ)2‐WPU, and Cd(5‐AQ)2‐WPU with different emission wavelengths of blue fluorescence are prepared by bonding Zn(5‐AQ)2, Cu(5‐AQ)2, and Cd(5‐AQ)2 to polyurethane chains as chain extenders, respectively. Noteworthily, with the increase of transition metal ion radius (Zn2+ < Cu2+ < Cd2+), the fluorescence emission wavelengths of the complexes showed different degrees of blue‐shift, and the blue‐shifted wavelengths showed a decreasing trend. Importantly, their fluorescence colors are blue‐shifted from blue‐green to blue with different emission wavelengths after accessing the polyurethane backbone, which has potential applications in the field of tuning white LED materials. The thermal decomposition temperatures of Zn(5‐AQ)2‐WPU, Cu(5‐AQ)2‐WPU, and Cd(5‐AQ)2‐WPU are above 220°C with good thermal stability, and their fluorescence lifetimes are prolonged by 8.817, 8.896, and 6.489 ns, respectively, compared with the complexes. Furthermore, WPU transition metal complexes with water as a dispersive medium have an antibacterial efficiency of up to 100% against Escherichia coli, which is an environmentally friendly antibacterial material with broad application prospects.

European Smalt in 17th-Century Japan: Porcelain Decoration and Sacred Art

Japanese art tradition, contrary to the case of China, is characterized by an efficient and continued, although mostly undocumented, use of smalt from the late 16th century onward. Recent studies have successfully identified this pigment, the cobalt-colored glass that spread throughout the Old Continent during the Renaissance period, as the coloring agent employed for overglaze-blue enameling on Japanese porcelains produced at the kilns of Arita (the porcelain production center of Japan) from the early 1640s until the 20th century. Fragmentary evidence of the use of smalt in Japanese sacred art has also been reported, yet its earliest incorporation into such a type of traditional art form could not be identified. In order to resolve this crucial issue, portable EDXRF was employed for the non-destructive analyses of Japanese porcelains and sacred images bearing blue decoration. Scientific analysis allowed, for the first time ever, to establish a clear timeline of smalt use. Furthermore, this evidence and the literature data both agree, leading to the identification of the origin of the blue material used on both art productions.

21‐1: Invited Paper: Analysis of Capacitance Characteristics of Highly Efficient Blue OLEDs by Impedance Spectroscopy

Blue phosphorescent materials typically have larger capacitance compared with commercialized blue fluorescent OLEDs. To improve capacitance‐related image quality issues, we need to reduce capacitance of devices without sacrificing other device's properties such as efficiency, lifetime, and operating voltage. In this study, we analyzed devices with phosphor sensitized TADF (PST) emission devices by impedance spectroscopy and revealed that the capacitance is largely affected by giant surface potential (GSP) of consisting layers. The influence of GSP on capacitance is sensitively changed by not only GSP value but also the position of GSP layers in the device. We revealed the effect of GSP of HTL, BIL etc. and explained the mechanism underlying on this phenomena based on device simulation.

Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries

Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries

Development and synthesis of anthracene-based fluorescence material for non-doped OLEDs

Efficient organic blue materials are essential to develop highly efficient organic light-emitting diodes. However, there is a challenge to commercialize efficient blue compounds due to the fundamentally wide band gap and the lack of pure blue emitters. In this study, the new anthracene-based fluorescent emitter, (4-(10-(4-(9H-carbazol-9-yl)-2-methylphenyl)anthracen-9-yl)-3-methylphenyl)diphenylphosphine oxide (CZm-AN-mPO) was designed and synthesized. The thermal, photophysical and electrochemical properties of the CZm-AN-mPO were systematically investigated. The CZm-AN-mPO exhibits a deep-blue emission at 425 nm and AIE property with a relatively narrow full-width at half maximum of 34 nm. The CZm-AN-mPO based non-doped devices show pure blue emission. The optimized OLEDs indicated maximum external efficiencies of 4.3% and 4.2% at emission layer thickness of 20 nm and 40 nm, respectively.

Blue aggregation-induced emission bipolar materials consisting of diphenylsulfone or benzophenone core and triphenylethene-carbazole fragments for highly efficient OLEDs

Bipolar derivatives having aggregation-induced emission (AIE) properties were synthesized in reactions of 4,4′-difluorobenzophenone, 4-fluorophenyl-phenylsulfone or bis(4-fluorophenyl)sulfone with prepared key starting materials: 1,1,2-triphenyl-2-(9H-carbazol-2-yl)ethylene or 1-(9H-carbazol-2-yl)-4-(1,2,2-triphenylethenyl)benzene. The objective materials have shown high thermal stabilities and can form amorphous layers having high glass transition temperatures in the region of 110–173 °C. The photoluminescence spectra of the prepared derivatives registered using tetrahydrofuran-water solutions demonstrated strong blue emissions, confirming their AIE property. Thin films of the compounds were tested in multilayer organic light-emitting diodes. The device using bis(4-{2-[4-(1,1,2-triphenylethylenyl)phenyl]carbazol-9-yl}phenyl)sulfone emitter (EM3) outperformed the other devices, achieving a peak efficiencies of 3.4 % (5.6 cd/A and 4.7 lm/W) with maximum luminance of about 11000 cd/m2. However OLED using 4-{2-[4-(1,1,2-triphenylethylenyl)phenyl]carbazol-9-yl}phenyl-phenylsulfone (EM2) as emitter demonstrated higher efficiency at higher luminance values. The maximum efficiencies of the device were obtained at a luminance value of about 100 cd/m2 and were recorded as 3.2 % (5.2 cd/A and 4.1 lm/W) with luminance of 17515 cd/m2.

Single component long-lived dynamic room temperature phosphorescence with large-scale preparation and visible light excitation

A pure organic room temperature phosphorescence (PORTP) luminogen named as DCP was successfully prepared and showed long room temperature phosphorescence (RTP) and afterglow lifetimes (3 ms and 4 s in sequence). Meanwhile, DCP showed high fluorescence (0.14) and RTP (0.39) quantum yields in crystalline state, simultaneously presented visible light excitation and dynamic RTP. By host-guest doping and optimization, Urea/DCP doping system emitted blue RTP, with RTP and afterglow lifetimes of 341 ms of 5 s in turn. Crystal analysis and theoretical calculations indicated H stacking, large spin orbit coupling constant, and small energy gap between the lowest singlet and triplet states result in long RTP lifetime and high quantum yield for DCP. Based on long phosphorescence emission, an advanced anti-counterfeiting pattern was constructed. As far as we know, it is the first report that such small molecules containing 3, 5-dicyanopyridine show long-lived RTP in both crystalline state and doping system. In this paper, not only ultralong and blue PORTP materials with the advantage of large-scale preparation, but also single component dynamic RTP, and RTP of visible light excitation were achieved.

Tailored efficient and reliable double luminescent layer hybrid WOLEDs via doping engineering

Doping engineering has been widely utilized to increase the efficiency of White organic light-emitting diodes (WOLEDs). In this study, a blue phosphor material named DMAC-DPS and an orange phosphor material named PO-01 are integrated into the host materials Bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO) and carbazole-based 4,4′-biscarbazole-p-biphenyl (CBP) by incorporating the principle of complementary color luminescence, resulting in a doped double-luminescent layer hybrid WOLED. The developed device structure consists of ITO/MoO3/TCTA/DPEPO:DMAC-DPS/CBP:PO-01 (or CBP:PO-01/DPEPO:DMAC-DPS)/TAZ/Alq3/LiF/Al. The transfer of energy between the host and guest materials is achieved by controlling the thickness and position of the emitting layer, leading to a more balanced emission of blue and yellow light and an overall increase in device efficiency. The developed WOLED exhibits a maximum current efficiency of 26.8 cd A−1, a power efficiency of 16.8 lm W−1, and an external quantum efficiency of 10.95%. The stable color coordinates of the device remains consistent, varying from (0.34, 0.40) to (0.33, 0.39) at brightness levels ranging from 100 to 1000 cd m−2. Technically, the incorporation of blue and orange phosphor materials into the host materials DPEPO and CBP, respectively, resulting in a doped double-luminescent layer hybrid WOLED, has shown a more balanced emission of blue and yellow light and resulted in increased efficiency. The reliable color coordinates corroborate the good color stability, making it a promising candidate for various applications. Furthermore, the controlled transfer of energy between the host and guest materials has led to a more balanced emission of blue and yellow light. Our developed doping engineering methods have shown potential for increased efficiency and good color stability, making the developed WOLED a promising candidate for various applications.

Real-time identification and visualization of Egyptian blue using modified night vision goggles

The possibility to use light in the visible spectrum to induce near-infrared luminescence in some materials, particularly Egyptian blue and related pigments, offers a significant advantage in terms of their detection. Since 2008, this property has been exploited to reveal the presence of those pigments even in tiny amounts on ancient and decayed surfaces, using a technical-photography method. This paper presents a new type of imaging device that enables real-time, easy, and inexpensive identification and mapping of Egyptian blue and related materials. The potential of the new tool is demonstrated by its effectiveness in detecting Egyptian blue within some prestigious sites: (a) Egyptian findings at Museo Egizio, Turin; (b) underground Roman frescoes at Domus Aurea, Rome; and (c) Renaissance frescoes by Raphael, Triumph of Galatea and Loggia of Cupid and Psyche, at Villa Farnesina, Rome. The device is based on night vision technology and allows an unprecedented fast, versatile, and user-friendly approach. It is employable by professionals including archeologists, conservators, and conservation scientists, as well as by untrained individuals such as students or tourists at museums and sites. The overall aim is not to replace existing photographic techniques but to develop a tool that enables rapid preliminary recognition, useful for planning the work to be carried out with conventional methods. The ability to immediately track Egyptian blue and related pigments, through real-time vision, photos, and videos, also provides a new kind of immersive experience (Blue Vision) and can foster the modern use of these materials in innovative applications and future technologies.