Multivalent Sulfur Vacancy-Rich NiCo2S4@MnO2 Urchin-Like Heterostructures for Ambient Electrochemical N2 Reduction to NH3.

Innovative advances in the exploitation of effective electrocatalytic materials for the reduction of nitrogen (N2) to ammonia (NH3) are highly required for the sustainable production of fertilizers and zero-carbon emission fuel. In order to achieve zero-carbon footprints and renewable NH3 production, electrochemical N2 reduction reaction (NRR) provides a favorable energy-saving alternative but it requires more active, efficient, and selective catalysts. In current work, sulfur vacancy (Sv)-rich NiCo2S4@MnO2 heterostructures are efficaciously fabricated via a facile hydrothermal approach followed by heat treatment. The urchin-like Sv-NiCo2S4@MnO2 heterostructures serve as cathodes, which demonstrate an optimal NH3 yield of 57.31 µg h-1 mgcat -1 and Faradaic efficiency of 20.55% at -0.2 V versus reversible hydrogen electrode (RHE) in basic electrolyte owing to the synergistic interactions between Sv-NiCo2S4 and MnO2. Density functional theory (DFT) simulation further verifies that Co-sites of urchin-like Sv-NiCo2S4@MnO2 heterostructures are beneficial to lowering the energy threshold for N2 adsorption and successive protonation. Distinctive micro/nano-architectures exhibit high NRR electrocatalytic activities that might motivate researchers to explore and concentrate on the development of heterostructures for ambient electrocatalytic NH3 generation.

Photo-Controllable Ultralong Room-Temperature Phosphorescence: State of the Art.

In this concept, we showcase the upsurge in the studies of dynamic ultralong room-temperature phosphorescence (RTP) materials containing inorganic and/or organic components as versatile photo-responsive platforms. The goal is to provide a comprehensive analysis of photo-controllable RTP, and meanwhile delve into the underlying RTP properties of various classes of photochromic materials including metal-organic complexes, organic-inorganic co-crystals, purely organic small molecules and organic polymers. In particular, the design principles governing the integration of the photochromic and RTP moieties within a single material system, and the tuning of dynamic RTP in response to light are emphasized. As such, this concept sheds light on the challenges and opportunities of using these tunable RTP materials for potential applications in optoelectronics, particularly highlighting their use of reversible information encryption, erasable light printing and rewritable smart paper.

Solid-State Photochemical Cascade Process Boosting Smart Ultralong Room-Temperature Phosphorescence in Bismuth Halides.

Molecular ultralong room-temperature phosphorescence (RTP), exhibiting multiple stimuli-responsive characteristics, has garnered considerable attention due to its potential applications in light-emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo-burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)-based metal-organic halide (MOH), a continuous and photo-responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi-based MOH, diverse application demonstrations, such as multi-mode anti-counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof-of-concept for the development of solid-state PCCPs that integrate photosalient effect and photochromism with light-chemical-mechanical energy conversion, but also lays the groundwork for designing new Bi-based MOHs with dynamically responsive ultralong RTP.

Synchronously Improved Multiple Afterglow and Phosphorescence Efficiencies in 0D Hybrid Zinc Halides with Ultrahigh Anti-Water Stabilities.

Zero-dimensional (0D) hybrid metal halides have been emerged as room-temperature phosphorescence (RTP) materials, but synchronous optimization of multiple phosphorescence performance in one structural platform remains less resolved, and stable RTP activity in aqueous medium is also unrealized due to serious instability toward water and oxygen. Herein, we demonstrated a photophysical tuning strategy in a new 0D hybrid zinc halide family of (BTPP)2ZnX4 (BTPP = benzyltriphenylphosphonium, X = Cl and Br). Infrequently, the delicate combination of organic and inorganic species enables this family to display multiple ultralong green afterglow and efficient self-trapped exciton (STE) associated cyan phosphorescence. Compared with inert luminescence of [BTPP]+ cation, incorporation of anionic [ZnX4]2- effectively enhance the spin-orbit coupling effect, which significantly boosts the photoluminescence quantum yield (PLQY) up to 30.66% and 54.62% for afterglow and phosphorescence, respectively. Synchronously, the corresponding luminescence lifetime extend to 143.94 ms and 0.308 µs surpassing the indiscernible phosphorescence of [BTPP]X salt. More importantly, this halide family presents robust RTP emission with nearly unattenuated PLQY in water and harsh condition (acid and basic aqueous solution) over half a year. The highly efficient integrated afterglow and STE phosphorescence as well as ultrahigh aqueous state RTP realize multiple anti-counterfeiting applications in wide chemical environments.

Macroscopic Assembly of Chiral Hydrogen-bonded Metal-free Supramolecular Glasses for Enhanced Color-tunable Ultralong Room Temperature Phosphorescence.

Glassy materials, with desirable mechanical rigidity, shaping ability, high transparency, are attracting great interest in diverse fields. However, optically bulk molecule-based glasses are still rare, mainly due to limited monomeric species and harsh preparation conditions. Herein, we report a facile bottom-up solution fabrication process to obtain metal-free supramolecular glasses (SMGs) at the macroscopic scale using L-Histidine and hexamethylenetetramine as building blocks. The chiral SMGs possess color-tunable ultralong room temperature phosphorescence (decay lifetime up to 141.2 ms) and circular polarized luminescence (g factor up to 8.7×10-3 ). The strong hydrogen bonds effectively drive the formation of SMGs, and provide a rigid microenvironment to boost triplet exciton generation. By virtue of excitation- and temperature-dependent ultralong phosphorescence of the SMGs, applications including multicolored displays, visual UV detection, and persistently luminescent thermometer are demonstrated.

Leveraging Crystalline and Amorphous States of a Metal-Organic Complex for Transformation of the Photosalient Effect and Positive-Negative Photochromism.

Uncovering differences between crystalline and amorphous states in molecular solids would both promote the understanding of their structure-property relationships, as well as inform development of multi-functional materials based on the same compound. Herein, for the first time, we report an approach to leverage crystalline and amorphous states of a zero-dimensional metal-organic complex, which exhibited negative and positive photochromism, due to the competitive chemical routes between photocycloaddition and photogenerated radicals. Furthermore, different polymorphs lead to the on/off toggling of photo-burst movement (photosalient effect), indicating the controllable light-mechanical conversion. Three demos were further constructed to support their application in information encryption and anti-counterfeiting. This work provides the proof-of-concept of a state- and polymorph-dependent photochemical route, paving an effective way for the design of new dynamically responsive systems.

Ultralow-loss Optical Waveguides through Balancing Deep-Blue TADF and Orange Room Temperature Phosphorescence in Hybrid Antimony Halide Microstructures.

Harnessing the potential of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is crucial for developing light-emitting diodes (LEDs), lasers, sensors, and many others. However, effective strategies in this domain are still relatively scarce. This study presents a new approach to achieving highly efficient deep-blue TADF (with a PLQY of 25 %) and low-energy orange RTP (with a PLQY of 90 %) through the fabrication of lead-free hybrid halides. This new class of monomeric and dimeric 0D antimony halides can be facilely synthesized using a bottom-up solution process, requiring only a few seconds to minutes, which offer exceptional stability and nontoxicity. By leveraging the highly adaptable molecular arrangement and crystal packing modes, the hybrid antimony halides demonstrate the ability to self-assemble into regular 1D microrod and 2D microplate morphologies. This self-assembly is facilitated by multiple non-covalent interactions between the inorganic cores and organic shells. Notably, these microstructures exhibit outstanding polarized luminescence and function as low-dimensional optical waveguides with remarkably low optical-loss coefficients. Therefore, this work not only presents a pioneering demonstration of deep-blue TADF in hybrid antimony halides, but also introduces 1D and 2D micro/nanostructures that hold promising potential for applications in white LEDs and low-dimensional photonic systems.

Metal-Halide Coordination Polymers with Excitation Wavelength- and Time-Dependent Ultralong Room-Temperature Phosphorescence.

Metal-organic hybrids with ultralong room-temperature phosphorescence (RTP) have potential applications in many fields, including optical communications, anticounterfeiting, encryption, bioimaging, and so on. Herein, we report two isostructural one-dimensional zinc-organic halides as coordination polymers ZnX2(bpp) (X = Cl, 1; Br, 2; bpp = 1,3-di(4-pyridyl)propane) with excitation wavelength- and time-dependent ultralong RTP properties. The dynamic multicolor afterglow can be assigned to the emission of the pristine ligand bpp and its interactions with halogen atoms. Experiments and theoretical calculations both suggest that ZnX2 is crucial for ultralong RTP: (a) the metal coordination and X...π bonds in coordination polymers fix the bpp molecules and suppress the nonradiative transitions; (b) the spin-orbital coupling of coordination polymers is largely enhanced relative to the bpp because of the heavy atom effect; and (c) the charge transfer exists between halogens and bpp ligand. Therefore, this work not only presents metal-halide coordination polymers with excitation wavelength- and time-dependent RTP properties, but also provides a facile method for the new types of dynamic multicolor afterglow materials.

Recent advances in persistent luminescence based on molecular hybrid materials.

Molecular persistently luminescent materials have received recent attention due to their promising applications in optical displays, biological imaging, chemical sensing, and security systems. In this review, we systematically summarize recent advances in establishing persistently luminescent materials-specifically focusing on materials composed of molecular hybrids for the first time. We describe the main strategies for synthesizing these hybrid materials, namely: (i) inorganics/organics, (ii) organics/organics, and (iii) organics/polymer systems and demonstrate how molecular hybrids provide synergistic effects, while improving luminescence lifetimes and efficiencies. These hybrid materials promote new methods for tuning key physical properties such as singlet-triplet excited state energies by controlling the chemical interactions and molecular orientations in the solid state. We review new advances in these materials from the perspective of examining experimental and theoretical approaches to room-temperature phosphorescence and thermally-activated delayed fluorescence. Finally, this review concludes by summarizing the current challenges and future opportunities for these hybrid materials.

Highly Efficient and Direct Ultralong All-Phosphorescence from Metal-Organic Framework Photonic Glasses.

Realizing efficient and ultralong room-temperature phosphorescence (RTP) is highly desirable but remains a challenge due to the inherent competition between excited state lifetime and photoluminescence quantum yield (PLQY). Herein, we report the bottom-up self-assembly of transparent metal-organic framework (MOF) bulk glasses exhibiting direct ultralong all-phosphorescence (lifetime: 630.15 ms) with a PLQY of up to 75 % at ambient conditions. These macroscopic MOF glasses have high Young's modulus and hardness, which provide a rigid environment to reduce non-radiative transitions and boost triplet excitons. Spectral technologies and theoretical calculations demonstrate the photoluminescence of MOF glasses is directly derived from the different triplet excited states, indicating the great capability for color-tunable afterglow emission. We further developed information storage and light-emitting devices based on the efficient and pure RTP of the fabricated MOF photonic glasses.

Dynamic Manipulating Space-Resolved Persistent Luminescence in Core-Shell MOFs Heterostructures via Reversible Photochromism.

Photo-controllable persistent luminescence at the single crystal level can be achieved by the integration of long-lived room temperature phosphorescence (RTP) and photochromism within metal-organic frameworks (MOFs) for the first time. Moreover, the multiblock core-shell heterojunctions have been prepared utilizing the isostructural MOFs through an epitaxial growth process, in which the shell exhibits bright yellow afterglow emission that gradually disappears upon further irradiation, but the core does not show such property. Benefitting from combined persistent luminescence and photochromic behavior, a multiple encryption demo can be facilely designed based on the dynamic manipulating RTP via reversible photochromism. This work not only develops new types of dynamically photo-controllable afterglow switch, but also provides a method to obtain MOFs-based optical heterojunctions towards potential space/time-resolved information encryption and anti-counterfeiting applications.

Light/Force-Sensitive 0D Lead-Free Perovskites: From Highly Efficient Blue Afterglow to White Phosphorescence with Near-Unity Quantum Efficiency.

Herein, new types of zero-dimensional (0D) perovskites (PA6InCl9 and PA4InCl7) with blue room-temperature phosphorescence (RTP) were obtained from InCl3 and aniline hydrochloride. These are highly sensitive to external light and force stimuli. The RTP quantum yield of PA6InCl9 can be enhanced from 25.2 % to 42.8 % upon illumination. Under mechanical force, PA4InCl7 exhibits a phase transform to PA6InCl9, thus boosting ultralong RTP with a lifetime up to 1.2 s. Furthermore, white and orange pure RTP with a quantum yield close to 100 % can be realized when Sb3+ was introduced into PA6InCl9. The white pure phosphorescence with a color-rendering index (CRI) close to 90 consists of blue RTP of PA6InCl9 and orange RTP of Sb3+ . Thus, this work not only overcomes long-standing problems of low quantum yield and short lifetime of blue RTP, but also obtains high-efficiency white RTP. It provides a feasible method to realize near-unity quantum efficiency and has great application potential in the fields of optical devices and smart materials.

Mo3 S13 2- Intercalated Layered Double Hydroxide: Highly Selective Removal of Heavy Metals and Simultaneous Reduction of Ag+ Ions to Metallic Ag0 Ribbons.

We demonstrate a new material by intercalating Mo3 S13 2- into Mg/Al layered double hydroxide (abbr. Mo3 S13 -LDH), exhibiting excellent capture capability for toxic Hg2+ and noble metal silver (Ag). The as-prepared Mo3 S13 -LDH displays ultra-high selectivity of Ag+ , Hg2+ and Cu2+ in the presence of various competitive ions, with the order of Ag+ >Hg2+ >Cu2+ >Pb2+ ≥Co2+ , Ni2+ , Zn2+ , Cd2+ . For Ag+ and Hg2+ , extremely fast adsorption rates (≈90 % within 10 min, >99 % in 1 h) are observed. Much high selectivity is present for Ag+ and Cu2+ , especially for trace amounts of Ag+ (≈1 ppm), achieving a large separation factor (SFAg/Cu ) of ≈8000 at the large Cu/Ag ratio of 520. The overwhelming adsorption capacities for Ag+ (qm Ag =1073 mg g-1 ) and Hg2+ (qm Hg =594 mg g-1 ) place the Mo3 S13 -LDH at the top of performing sorbent materials. Most importantly, Mo3 S13 -LDH captures Ag+ via two paths: a) formation of Ag2 S due to Ag-S complexation and precipitation, and b) reduction of Ag+ to metallic silver (Ag0 ). The Mo3 S13 -LDH is a promising material to extract low-grade silver from copper-rich minerals and trap highly toxic Hg2+ from polluted water.

Research Progress in Organic Synthesis by Means of Photoelectrocatalysis.

The rapid development of radical chemistry has spurred several innovative strategies for organic synthesis. The novel approaches for organic synthesis play a critical role in promoting and regulating the single-electron redox activity. Among them, photoelectrocatalysis (PEC) has attained considerable attention as the most promising strategy to convert organic compounds into fine chemicals. This review highlights the current progress in organic synthesis through PEC, including various catalytic reactions, catalyst systems and practical applications. The numerous catalytic reactions suffer the high overpotential and poor conversion efficiency, depending on the design of electrolyzers and the reaction mechanisms. We also considered the recent developments with special emphasis on scientific problems and efficient solutions, which enhance accessibility to utilize and further develop the photoelectrocatalytic technology for the specific chemical bonds formation and the fabrication of numerous catalytic systems.

Mechanistic In Situ and Ex Situ Studies of Phase Transformations in Molecular Co-Crystals.

Co-crystallisation is widely explored as a route to improve the physical properties of pharmaceutical active ingredients, but little is known about the fundamental mechanisms of the process. Herein, we apply a hyphenated differential scanning calorimetry-X-ray diffraction technique to mimic the commercial hot melt extrusion process, and explore the heat-induced synthesis of a series of new co-crystals containing isonicotinamide. These comprise a 1:1 co-crystal with 4-hydroxybenzoic acid, 2:1 and 1:2 systems with 4-hydroxyphenylacetic acid and a 1:1 crystal with 3,4-dihydroxyphenylactic acid. The formation of co-crystals during heating is complex mechanistically. In addition to co-crystallisation, conversions between polymorphs of the co-former starting materials and co-crystal products are also observed. A subsequent study exploring the use of inkjet printing and milling to generate co-crystals revealed that the synthetic approach has a major effect on the co-crystal species and polymorphs produced.

Manipulating Light-Induced Dynamic Macro-Movement and Static Photonic Properties within 1D Isostructural Hydrogen-Bonded Molecular Cocrystals.

Smart molecular crystals with light-driven mechanical responses have received interest owing to their potential uses in molecular machines, artificial muscles, and biomimetics. However, challenges remain in control over both the dynamic photo-mechanical behaviors and static photonic properties of molecular crystals based on the same molecule. Herein, we show the construction of isostructural co-crystals allows their light-induced cracking and jumping behaviors (photosalient effect) to be controlled. Hydrogen-bonded co-crystals from 4-(1-naphthylvinyl)pyridine (NVP) with co-formers (tetrafluoro-4-hydroxybenzoic acid (THA) and tetrafluorobenzoic acid (TA)) crystallize as isostructural crystals, but have different static and dynamic photo-mechanical behaviors. These differences are due to alternations in the orientation of NVP and hydrogen-bonding modes of the co-formers. After light activation, the 1D NVP-TA crystal splits and shears off within 1 s. For NVP-THA, its photostability and high quantum yield give novel photonic properties, including low optical waveguide loss, highly polarized anisotropy, and efficient up-conversion fluorescence.

C60-Adsorbed Single-Walled Carbon Nanotubes as Metal-Free, pH-Universal, and Multifunctional Catalysts for Oxygen Reduction, Oxygen Evolution, and Hydrogen Evolution.

Buckminsterfullerene (C60) was adsorbed onto single-walled carbon nanotubes (SWCNTs) as an electron-acceptor to induce intermolecular charge-transfer with the SWCNTs, leading to a class of new metal-free C60-SWCNT electrocatalysts. For the first time, these newly developed C60-SWCNTs were demonstrated to act as trifunctional metal-free catalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) over a wide range of pH values, from acid to alkaline, with even higher electrocatalytic activities and better long-term stabilities than those of commercial Pt and RuO2 counterparts. Thus, the adsorption-induced intermolecular charge-transfer with the C60 electron-acceptor can provide a general approach to high-performance, metal-free, pH-universal carbon-based trifunctional metal-free electrocatalysts for water-splitting and beyond.

Simultaneous Long-Persistent Blue Luminescence and High Quantum Yield within 2D Organic-Metal Halide Perovskite Micro/Nanosheets.

Molecular solid-state materials with long-lived luminescence (such as thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) systems) are promising for display, sensoring, and bio-imaging applications. However, the design of such materials that exhibit both long luminescent lifetime and high solid-state emissive efficiency remains an open challenge. Two-dimensional (2D) organic-metal halide perovskite materials have a high blue-emitting quantum yield of up to 63.55 % and ultralong TADF lifetime of 103.12 ms at ambient temperature and atmosphere. Our design leverages the combined influences of a 2D space/electronic confinement effect and a modest heavy-atom tuning strategy. Photophysical studies and calculations reveal that the enhanced quantum yield is due to the rigid laminate structure of perovskites, which can effectively inhibit the non-radiative decay of excitons.

Recent Advances in Micro-/Nanostructured Metal-Organic Frameworks towards Photonic and Electronic Applications.

Micro- and nanometer-sized metal-organic frameworks (MOFs) materials have attracted great attention due to their unique properties and various potential applications in photonics, electronics, high-density storage, chemo-, and biosensors. The study of these materials supplies insight into how the crystal structure, molecular components, and micro-/nanoscale effects can influence the performance of inorganic-organic hybrid materials. In this Minireview article, we introduce recent breakthroughs in the controlled synthesis of MOF micro-/nanomaterials with specific structures and compositions, the tunable photonic and electronic properties of which would provide a novel platform for multifunctional applications. Firstly, the design strategies for MOFs based on self-assembly and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low-dimensional MOF micro-/nanostructures. Their new applications including two-photon excited fluorescence, multi-photon pumped lasing, optical waveguides, nonlinear optical (NLO), and field-effect transistors are also outlined. Finally, we briefly discuss perspectives on the further development of these hybrid crystalline micro-/nanomaterials.

Lanthanide Metal-Organic Framework Microrods: Colored Optical Waveguides and Chiral Polarized Emission.

Lanthanide metal-organic frameworks (Ln-MOFs) have received much attention owing to their structural tunability and widely photofunctional applications. However, successful examples of Ln-MOFs with well-defined photonic performances at micro-/nanometer size are still quite limited. Herein, self-assemblies of 1,3,5-benzenetricarboxylic acid (BTC) and lanthanide ions afford isostructural crystalline Ln-MOFs. Tb-BTC, Eu@Tb-BTC, and Eu-BTC have 1D microrod morphologies, high photoluminescence (PL) quantum yields, and different emission colors (green, orange, and red). Spatially PL resolved spectra confirm that Ln-MOF microrods exhibit an optical waveguide effect with low waveguide loss coefficient (0.012≈0.033 dB µm-1 ) during propagation. Furthermore, these microrods feature both linear and chiral polarized photoemission with high anisotropy.