Regulation of quantum spin conversions in a single molecular radical.

Free radicals, generally formed through the cleavage of covalent electron-pair bonds, play an important role in diverse fields ranging from synthetic chemistry to spintronics and nonlinear optics. However, the characterization and regulation of the radical state at a single-molecule level face formidable challenges. Here we present the detection and sophisticated tuning of the open-shell character of individual diradicals with a donor-acceptor structure via a sensitive single-molecule electrical approach. The radical is sandwiched between nanogapped graphene electrodes via covalent amide bonds to construct stable graphene-molecule-graphene single-molecule junctions. We measure the electrical conductance as a function of temperature and track the evolution of the closed-shell and open-shell electronic structures in real time, the open-shell triplet state being stabilized with increasing temperature. Furthermore, we tune the spin states by external stimuli, such as electrical and magnetic fields, and extract thermodynamic and kinetic parameters of the transition between closed-shell and open-shell states. Our findings provide insights into the evolution of single-molecule radicals under external stimuli, which may proof instrumental for the development of functional quantum spin-based molecular devices.

Open-Shell Diradical-Sensitized Electron Transport Layer for High-Performance Colloidal Quantum Dot Solar Cells.

The zinc oxide (ZnO) nanoparticles (NPs) are well-documented as an excellent electron transport layer (ETL) in optoelectronic devices. However, the intrinsic surface flaw of the ZnO NPs can easily result in serious surface recombination of carriers. Exploring effective passivation methods of ZnO NPs is essential to maximize the device's performance. Herein, a hybrid strategy is explored for the first time to improve the quality of ZnO ETL by incorporating stable organic open-shell donor-acceptor type diradicaloids. The high electron-donating feature of the diradical molecules can efficiently passivate the deep-level trap states and improve the conductivity of ZnO NP film. The unique advantage of the radical strategy is that its passivation effectiveness is highly correlated with the electron-donating ability of radical molecules, which can be precisely controlled by the rational design of molecular chemical structures. The well-passivated ZnO ETL is applied in lead sulfide (PbS) colloidal quantum dot solar cells, delivering a power conversion efficiency of 13.54%. More importantly, as a proof-of-concept study, this work will inspire the exploration of general strategies using radical molecules to construct high-efficiency solution-processed optoelectronic devices.

Accessing Highly Efficient Photothermal Conversion with Stable Open-Shell Aromatic Nitric Acid Radicals.

It is very challenging to prepare stable radicals as they are usually thermodynamically or kinetically unstable in air. Herein, a series of star-shaped aromatic nitric acid radicals were prepared via facile demethylation and consequent oxidation. As phenol radicals without steric hindrance group protection, they exhibit high electrochemical and thermal stability due to their rich resonance structures including closed-shell nitro-like and open-shell nitroxide structure with unpaired electrons delocalized in conjugated backbones. Among them, TPA-TPA-O6 powder exhibited extremely wide absorption from 300 to 2000 nm covering the whole solar spectral irradiance, high photothermal conversion efficiency, and negligible photobleaching effect in seawater desalination. Under the irradiation of one sunlight, the water evaporation efficiency of TPA-TPA-O6 is recorded to be as high as 89.41 % and the water evaporation rate is 1.293 kg m-2 h-1 , which represents the top performance in pure organic small molecule photothermal materials.

Aggregation-Induced Radical of Donor-Acceptor Organic Semiconductors.

Narrow bandgap donor-acceptor organic semiconductors are generally considered to show a closed-shell singlet ground state, and their radicals are reported as impurities, defects, polarons, and charge transfer monoradicals. Herein, we systematically investigated the open-shell singlet diradical electronic ground state of two diketopyrrolopyrrole-based compounds via the combination of electron spin resonance (ESR), nuclear magnetic resonance, superconducting quantum interference device magnetometry, and theoretical calculations. It is widely known that the quinoidal character will be significantly enhanced in the aggregation state accompanied by improved planarity and enhanced delocalization. We proposed an aggregation-induced radical and captodative effect as the driving force for the formation and stabilization of the open-shell quinoid diradical based on the ESR test in different proportions of mixed solvents. Our results provided a novel view for understanding the intrinsic chemical structure of donor-acceptor organic semiconductors, the open-shell singlet and thermally excited triplet electronic states, and the unexpected physical processes between the ground state and the excited state.

Evolution of the electronic structure in open-shell donor-acceptor organic semiconductors.

Most organic semiconductors have closed-shell electronic structures, however, studies have revealed open-shell character emanating from design paradigms such as narrowing the bandgap and controlling the quinoidal-aromatic resonance of the π-system. A fundamental challenge is understanding and identifying the molecular and electronic basis for the transition from a closed- to open-shell electronic structure and connecting the physicochemical properties with (opto)electronic functionality. Here, we report donor-acceptor organic semiconductors comprised of diketopyrrolopyrrole and naphthobisthiadiazole acceptors and various electron-rich donors commonly utilized in constructing high-performance organic semiconductors. Nuclear magnetic resonance, electron spin resonance, magnetic susceptibility measurements, single-crystal X-ray studies, and computational investigations connect the bandgap, π-extension, structural, and electronic features with the emergence of various degrees of diradical character. This work systematically demonstrates the widespread diradical character in the classical donor-acceptor organic semiconductors and provides distinctive insights into their ground state structure-property relationship.

Phenoxy Radical-Induced Formation of Dual-Layered Protection Film for High-Rate and Dendrite-Free Lithium-Metal Anodes.

The uncontrollable dendrite growth of Li metal anode leads to poor cycle stability and safety concerns, hindering its utilization in high energy density batteries. Herein, a phenoxy radical Spiro-O8 is proposed as an artificial protection film for Li metal anode owing to its excellent film-forming capability and remarkable ionic conductivity. A spontaneous redox reaction between the Spiro-O8 and Li metal results in the formation of a uniform and highly ionic conductive organic film in the bottom. Meanwhile, the phenoxy radicals on surface of Spiro-O8 facilitate the decomposition of Li salt upon exposed to the ether electrolyte and lead the formation of LiF film on the top. Arising from the synergistic effects of inner high ionic conductive film and outer rigid film, stable Li plating/stripping can be realized at a high current density (4000 cycles at 10 mA cm-2 ) and a high areal capacity of 5 mAh cm-2 for 550 h with an ultrahigh Li utilization rate of 54.6 %. As a proof of concept, this work shows a facile strategy to rationally fabricate dual-layered interfaces for Li metal anodes.

Mechanisms of pattern and colour generation of Chinese Tianmu glaze.

Tianmu glaze wares are a very famous form of ancient Chinese porcelain. The samples were prepared with local raw materials and traditional technology. X-ray diffraction, scanning electron microscopy, optical microscopy and energy dispersive spectroscopy were used to analyse the phase composition, microstructure and chemical composition of the Tianmu glaze. The results show that the patterns were created by the process that includes phase separation, the iron-rich phase moving to the surface, the growth of nanosized magnetite and hematite crystals, the aggregation of a thin crystal layer, and the appearance and collapse of bubbles. Scattering, diffraction and interference of nanosized grains are the primary colour rendering mechanism.

Preparation of high permeable alumina ceramic membrane with good separation performance via UV curing technique.

The traditional dip-coating method for preparation of ceramic membranes requires a long drying time and easily produces drying defects. In this work, an improved dip-coating process was proposed. The UV curing technique was utilized to avoid crack formation and agglomeration of ceramic particles, for drying to be completed in a few minutes. Photosensitive resin and a photoinitiator were added into the aqueous ceramic suspension. Under the action of free radicals excited by ultraviolet light, a giant network formed in the green membrane within a short time which limits the migration of membrane particles. Experiments were performed to explore the influence of UV curing process on membrane properties and the optimum preparation conditions were obtained. Following a rapid drying treatment and firing, crack-free membranes were prepared, which exhibited a narrow pore size distribution centered at approximately 65.2 nm and a water permeance of 887 ± 48 L m-2 h-1 bar-1. The largest pore size of the membrane was 85.7 nm while it could filter out 98.2% of the 100 nm monosize PS microsphere and the 60.1% of 60 nm, indicating its potential application in both membrane production efficiency and separation accuracy improvements.

Preparation and mechanism analysis of high performance ceramic membrane by spray coating.

A spray coating method was proposed to fabricate an α-Al2O3 micro-filtration membrane with excellent performance. It was observed that air gaps could form inside the support during the coating stage that effectively prevent membrane forming particles from penetrating into the support without an intermediate layer. Thus the pure water permeability of the membrane with average pore size of 0.13 µm and thickness of 25.46 µm could reach 2893 Lm-2 h-1 bar-1. The effects of firing conditions, membrane thickness and backwash or backpulse conditions on the pore size distribution of the membrane were investigated. Meanwhile the prepared membrane could sustain good filtration performance and mechanical integrity during backpulsing and backwashing processes under the transmembrane pressure (TMP) of 8 bar, which also exhibited a rejection rate of 98.8% for the carbon ink with an average particle size of 164 nm.