Coupling Au with BO_(x) matrix induced by Closo-boron cluster for electrochemical synthesis of ammonia

Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.

Accurate quantification of TiO_(2)(B)'s phase purity via Raman spectroscopy

Bronze phase titanium dioxide(TiO_(2)(B))could be a promising high-power anode for lithium ion battery.However,TiO_(2)(B)is a metastable material,so the as-synthesized samples are inevitably accompanied by the existence of anatase phases.It has been found that the TiO_(2)(B)'s purity is positively correlated with its electrochemical performance.Herein,we have established an accurate quantification of the TiO_(2)(B)/anatase ratio,by figuring out the function between the purity of TiO_(2)(B)phase in the high purity range and its Raman spectra features in combination of the calibration by the synchrotron radiation X-ray diffraction(XRD).Compared with the time-consuming electrochemical method,the rapid,sensitive and non-destructive features of Raman spectroscopy have made it a promising candidate for determining the purity of TiO_(2)(B).Further,the correlations developed in this work should be instructive in synthesizing pure TiO_(2)(B)and furthermore optimizing its electrochemical charge storage properties.

Towards Solar-Driven Formation of Robust and Self-Healable Waterborne Polyurethane Containing Disulfide Bonds via in-situ Incorporation of 2D Titanium Carbide MXene

Waterborne polymers are vital for coating industry to reduce carbon emissions.However,formation of robust and self-healable films at ambient temperature remains a challenge owing to high energy cost of film formation process.This work reports a solar-driven film formation of waterborne polyurethanes(WPUs)containing disulfide bonds via in-situ incorporation of 2D titanium carbide(MXene)with ability to convert light to heat.Instead of directly mixed with WPUs,MXene is added to join the reaction with isocyanate-terminated pre-polymer before emulsification process.This approach not only prevents aggregation of MXene in water but stabilizes MXene against thermal degradation which is the key hurdle for mass production of MXene/WPU composites.More importantly,our results show that mechanical performance of WPU films under visible light(100 mW/cm^(2))is overwhelmingly competitive with that processed in oven.Furthermore,the existence of disulfide bonds in PU chains enables fast self-healing of micro-cracks under natural visible light which could vanish completely within 40 min.The fractured specimens were repaired under natural visible light for 2 h,and the self-healing efficiency of tensile strength and elongation at break reached over 94.00%.

Achieving highly efficient long-wavelength phosphorescence emission of large singlet-triplet energy gap materials by host-guest doping

High-efficiency long-wavelength phosphorescence emissions of large singlet-triplet energy gap(ΔE_(ST))materials are essential for applications in biology and display.However,few long-wavelength phosphorescence emissions of largeΔE_(ST)materials have been reported due to the weak spin-orbit coupling(SOC)and strong non-radiative transitions.Herein,we develop a strategy to achieve highly efficient long-wavelength room temperature phosphorescence(RTP)emission of largeΔE_(ST)materials,which display bright red RTP emission with above 400μs lifetime and 6.5%phosphorescent quantum efficiency.Our experiments and theoretical calculations reveal that the fishbone-like packing and the zig-zag interactions provide favorable conditions for suppressing the non-radiative transitions of triplet state excitons,and heavy atoms effectively promote the intersystem crossing(ISC)process for highly efficient long-wavelength phosphorescence emission.The universality of the method for highly efficient long-wavelength RTP emission of largeΔE_(ST)materials was further investigated in various guests.Moreover,these materials with largeΔE_(ST)manifest the advantages of large color contrast on the display and utilization potentiality in information encryption.This strategy paves the way for the high contrast display and development of information encryption with RTP emission.

Recent Developments of Photodeformable Polymers:From Materials to Applications

Photodeformable polymer materials have a far influence in the fields of flexibility and intelligence.The stimulation energy is converted into mechanical energy through molecular synergy.Among kinds of photodeformable polymer materials,liquid crystalline polymer(LCP)photodeformable materials have been a hot topic in recent years.Chromophores such as azobenzene,a-cyanostilbene,and 9,10-dithiopheneanthracene have been widely used in LCP,which are helpful for designing functional molecules to increase the penetration depth of light to change physical properties.Due to the various applications of photodeformable polymer materials,there are many excellent reports in intelligent field.In this review,we have systematized LCP containing azobenzene into 3 categories depending on the degree of crosslinking liquid crystalline elastomers,liquid crystalline networks,and linear LCPs.Other structural,typical polymer materials and their applications are discussed.Current issues faced and future directions to be developed for photodeformable polymer materials are also summarized.

Catalysis-based specific detection and inhibition of tyrosinase and their application

Tyrosinase is an important enzyme in controlling the formation of melanin in melanosome,and plays a key role in the pigmentation of hair and skin.The abnormal expression or activation of tyrosinase is associated with several diseases such as albinism,vitiligo,melanoma and Parkinson disease.Excessive deposition of melanin could cause diseases such as freckles and brown spots in the human body,and it is also closely related to browning of fruits and vegetables and insect molting.Detecting and inhibiting the activity of tyrosinase is of extraordinary value in the progress of diagnosis and treatment of these diseases.Therefore,many selective optical detection probes and small molecular inhibitors have been developed,and have made significant contributions to the basic and clinical research on these diseases.In this paper,the detection and inhibition of tyrosinase and their application in whitening products are reviewed,with special emphasis on development of fluorescent probes and inhibitors.Hopefully,this review will help design more efficient and sensitive tyrosinase probes and inhibitors,as well as shed light on novel treatment of diseases such as melanoma.

Recent advances and prospects of asymmetric non-fullerene small molecule acceptors for polymer solar cells

Recently,polymer solar cells developed very fast due to the application of non-fullerence acceptors.Substituting asymmetric small molecules for symmetric small molecule acceptors in the photoactive layer is a strategy to improve the performance of polymer solar cells.The asymmetric design of the molecule is very beneficial for exciton dissociation and charge transport and will also fine-tune the molecular energy level to adjust the open-circuit voltage(Voc)further.The influence on the absorption range and absorption intensity will cause the short-circuit current density(Jsc)to change,resulting in higher device performance.The effect on molecular aggregation and molecular stacking of asymmetric structures can directly change the microscopic morphology,phase separation size,and the active layer's crystallinity.Very recently,thanks to the ingenious design of active layer materials and the optimization of devices,asymmetric non-fullerene polymer solar cells(A-NF-PSCs)have achieved remarkable development.In this review,we have summarized the latest developments in asymmetric small molecule acceptors(A-NF-SMAs)with the acceptor-donor-acceptor(A-D-A)and/or acceptor-donor-acceptor-donor-acceptor(A-D-A-D-A)structures,and the advantages of asymmetric small molecules are explored from the aspects of charge transport,molecular energy level and active layer accumulation morphology.

Tuning crystal orientation and charge transport of quasi-2D perovskites via halogen-substituted benzylammonium for efficient solar cells

Quasi-two-dimensional(quasi-2D)perovskites with high stability usually suffers from poor device efficiency.Chemical tuning of the spacer cations has been an effective strategy to achieve efficient and stable quasi-2D perovskite solar cells.Here,we demonstrate that 3-halogon-substituted benzylammonium iodide(3X-BAI,X=F,Cl,Br,I)can significantly affect the orientation of low-dimensional perovskites and charge transport from perovskite to hole extraction layer,as well as device performance.With 3Br-BAI,we achieve the highest device efficiency of 13.21%for quasi-2D perovskites with a nominal n=3 average composition.Our work provides a facile approach to regulate vertical crystal orientation and charge transport via tuning the molecular structure of organic spacer toward high performance quasi-2D perovskite solar cells.

Computational Insights into Charge Storage Mechanisms of Supercapacitors

Computational modeling methods,including molecular dynamics(MD)and Monte Carlo(MC)simulations,and density functional theory(DFT),are receiving booming interests for exploring charge storage mechanisms of electrochemical energy storage devices.These methods can effectively be used to obtain molecular scale local information or provide clear explanations for novel experimental findings that cannot be directly interpreted through experimental investigations.This short review is dedicated to emphasizing recent advances in computational simulation methods for exploring the charge storage mechanisms in typical nanoscale materials,such as nanoporous carbon materials,2 D MXene materials,and metal-organic framework electrodes.Beyond a better understanding of charge storage mechanisms and experimental observations,fast and accurate enough models would be helpful to provide theoretical guidance and experimental basis for the design of new high-performance electrochemical energy storage devices.

Controllable assembling of highly-doped linked carbon bubbles on graphene microfolds

Carbon-based microassemblies(CMs) have attracted significant attention in numerous applications due to their unique hierarchical structures and delicate building blocks,especially when hollow carbon spheres(HCSs) are reasonably introduced into the construction.Herein,a new design for novel HCSscombined CMs is proposed.Remarkably,the HCSs are linear carbon bubbles linked one-by-one, arranging into necklaces decorating on the graphene microfolds.Detailed thermal analysis confirm that high temperatures straighten the linked carbon bubbles into bamboo-like carbon nanofibers,evidently due to the attenuation of doping degree.Benefiting from the abundant active sites of carbon bubbles,the obtained CMs exhibit satisfactory electrocatalytic activity for oxygen reduction reactions.This work establishes a bridge to precisely control the synthesis of carbon-based hierarchical architectures.

Approaching Superior Potassium Storage of Carbonaceous Anode Through a Combined Strategy of Carbon Hybridization and Sulfur Doping

Carbonaceous materials are promising anode candidates for potassium-ion batteries(PIBs)given its high conductivity,stable property,and abundant resource,while its practical implementation is still hampered by its limited capacity and inferior rate behavior.Herein,we report a superior carbonaceous anode through a combined strategy of carbon hybridization and heteroatom doping.In this composite,hollow carbon spindles(HCS)were anchored on the surface of graphene(G)followed with sulfur doping treatment,aiming to integrate the high conductivity of graphene,the good structure stability of HCS,and the S doping-induced ample active sites.As a PIB anode,the S-G@HCS composite can display high capacity(301 mAh g^(-1)at 0.1 A g^(-1)after 500 cycles)and long-term cyclability up to 1800 cycles at 2 A g^(-1).Impressively,it can deliver an outstanding rate capacity of 215 mAh g^(-1)at 10 A g^(-1),which is superior to most carbon anodes as-reported so far for PIBs.Experimental and theoretical analysis manifests that the construction of graphene/amorphous carbon interface as well as S doping enables the regulation of electronic structure and ion adsorption/transportation properties of carbonaceous material,thus accounting for the high capacity and superior rate capability of S-G@HCS composite.

Thiourea-assisted coating of dispersed copper electrocatalysts on Si photocathodes for solar hydrogen production

Photoelectrochemical water splitting can convert solar energy into clean hydrogen energy for storage.It is desirable to explore non-precious electrocatalysts for practical applications of a photoelectrode in a large scale.Here,we developed a facile spin-coating and in-situ photoelectrochemical reduction method to prepare a dispersed Cu electrocatalyst on a Si photocathode,which improves the performance remarkably.We find that thiourea in the precursor solution for spin-coating plays an important role in obtaining dispersed Cu particles on the surface of a Si photoelectrode.With thiourea in the precursor,the Cu/Si photocathode shows higher performance than the one without thiourea.Moreover,the Cu/Si photocathode also indicates good stability after 16 h illumination.

Crystalline framework nanosheets as platforms for functional materials

The integration of organic and inorganic materials has been widely used in various applications to generate novel functional nanomaterials characterized by unique properties.Functional crystalline framework nanosheets and their synergistic effects have been studied recently for possessing the advantages of functional species as well as crystalline framework nanosheets.Hence,we have focused on the preparation methods and applications of functional crystalline framework nanosheets in this review.We introduced crystalline framework nanosheets and discussed the importance of integrating functional species with nanosheets to form functional crystalline framework nanosheets.Then,two aspects of the preparation methods of functional crystalline framework nanosheets were reviewed:in situ synthesis and post-synthesis modification.Subsequently,we discussed the properties of the crystalline framework nanosheets combined with various functional species and summarized their applications in catalysis,sensing,separation,and energy storage.Finally,we have shared our insights on the challenges of functional crystalline framework nanosheets,hoping to contribute to the knowledge base for optimizing the preparation methods,expanding categories,improving stability,and exploring potential applications.

An ultra-porous g-C_(3)N_(4) micro-tube coupled with MXene(Ti_(3)C_(2)TX)nanosheets for efficient degradation of organics under natural sunlight

It remains as a challenge for realizing efficient photo-responsive catalysts towards largescale degradation of organic pollutants under natural sunlight.This work reports a new pore engineering strategy for creating ultra-porous g-C_(3)N_(4) micro-tubes with an unprecedentedly high specific surface area of 152.96 m^(2)/g.This is mainly associated with releasing internal vapor pressure in the autoclave where the hydrothermal treatment of the urea/melamine mixture is processed.Supported by microscopic observation,porosity measurement and spectroscopic characterization,it is found that releasing the pressure at halfway of hydrothermal process is vital for forming exfoliated rod-like precursors and the de-aggregation of these rods presents substantial benefits on the production of mesopores on g-C_(3)N_(4) microtubes during the calcination of precursors.This offers a large number of reactive sites required by photocatalytic reaction.Coupling these micro-tubes with Ti_(3)C_(2)T_(X) nanosheets via electrostatic interaction yields a 1D/2D heterojunction with a close interfacial contact.The addition of metallically conductive Ti_(3)C_(2)T_(X) nanosheets accelerates the separation between electrons and holes,and also enhances the light absorption.All these merits of structural design lead to forming a group of highly efficient catalysts demonstrating an excellent photocatalytic degradation rate of k=0.0560 min^(-1)for RhB dyes under 100 mW/cm~2 visible light radiation that micks sunlight outdoors.This laboratory valuation is further supported by an outdoor test that shows a fast degradation rate of 0.0744 min^(-1)under natural sunlight.

Ultrafast photoexcitation dynamics behavior of hydrogen-bonded polyfluorenol

Exciton behavior is crucial to the exploitation of light-emitting conjugated polymer(LCPs)for optoelectronic devices.Singlet excitons are easily trapped by the intrinsically defect structures.Herein,we set a polyfluorenol(PPFOH)as an example to systematically investigate its photophysical behavior to check the role of defect structures in LCPs.According to time-resolved photoluminescence analysis,the feature emission peaks from individual chain of PPFOH in diluted DMF solution is effectively avoided the influence of fluorenone formation,but the residual green-band emission at 550nm is easily observed in the PL spectra of PPFOH dilute toluene solution obtained delay 1.5 ns,confirmed the formation of“guest”physical aggregation-induced defect structure.Remarkably,efficient and ultrafast energy transfer from individual chain to defect structure is observed in PPFOH films.Interestingly,the efficient energy transfer happened for the film obtained from DMF solution(200 ps)than those of toluene ones(600 ps).Meanwhile,compared to relatively stable green-band emission in PPFOH film from toluene solution,red-shifted emission peak(11 nm)of PPFOH film from DMF solutions exposed to saturated DNT vapor also confirmed their different aggregation-induced green-band emission.Therefore,this aggregation defect structures are influenced on the photophysical property of LCPs in solid states.

Tailored multifunctional hydrazine derivatives for efficient printable hole-conductive-free mesoscopic perovskite solar cells via enhancing defect passivation

The low-cost and easy large-scale fabrication advantages of printable mesoscopic perovskite solar cells(p-MPSCs)are overshadowed by their limited photovoltaic conversion efficiency(PCE).Here,we introduce the hydrazide derivative of 4-Hydroxybenzoylhydrazine(4-HBH)to improve the PCE of p-MPSCs by inducing enhanced defect passivation.Both carbonyl and hydrazine groups in hydrazide groups present strong interaction with perovskite.The hydroxyl group,as an electron donor group,increases the electron cloud density of the hydrazide group in 4-HBH under the conjugation of the benzene ring,and thus enhances its interaction with perovskite.Additionally,the hydroxy group itself interacts with perovskite and passivates defects synergistically.The hydrazine agents can also reduce I2and suppress the loss of iodine in perovskite films,which inhibits the formation of iodine-related defects.Consequently,p-MPSCs with 4-HBH achieve a high PCE of 19.21%,and present well improved stability.

Phenylfluorenamine-functionalized poly(N-vinylcarbazole)s as dopant-free polymer hole-transporting materials for inverted quasi-2D perovskite solar cells

In order to improve the efficiency and stability of inverted three-dimensional(3D) or quasi-2D perovskite solar cells(PSCs) for future commercialization, exploring high efficient dopant-free polymer holetransporting materials(HTMs) is still desired and meaningful. One simple and efficient way to achieve high performance dopant-free HTMs is to synthesize novel non-conjugated side-chain polymers via rational molecular design. In this work, N-(4-methoxyphenyl)-9,9-dimethyl-9H-fluoren-2-amine(FMeNPh) groups are introduced into the poly(N-vinylcarbazole)(PVK) side chains to afford two nonconjugated polymers PVCz-DFMeNPh and PVCz-FMeNPh as dopant-free HTMs in inverted quasi-2D PSCs. Benefited from the flexible properties of polyethylene backbone and excellent optoelectronic natures of FMeNPh side-chain groups, PVCz-DFMeNPh with more FMeNPh units exhibited excellent thermal stability, well-matched energy levels and improved charge mobility as compared to PTAA and PVCzFMeNPh. Moreover, the morphologies investigation of quasi-2D perovskite on PVCz-DFMeNPh shows more compact and homogeneous perovskite films than those on PTAA and PVCz-FMeNPh. As a result,the dopant-free PVCz-DFMeNPh based inverted quasi-2D PSCs deliver power conversion efficiency(PCE) up to 18.44% as well as negligible hysteresis and favorable long-term stability, which represents as excellent performance reported to date for inverted quasi-2D PSCs. The results demonstrate the great potentials of constructing non-conjugated side-chain polymer HTMs based on phenylfluorenamine-func tionalized PVK for the development of high efficient and stable inverted 3D or quasi-2D PSCs.

Fluorine substitution position effects on spiro(fluorene-9,9’-xanthene) cored hole transporting materials for high-performance planar perovskite solar cells

Fluorine substitution in molecular design has become an effective strategy for improving the overall performance of organic photovoltaics.In this study,three low-cost small molecules of spiro-linked hole transporting materials(SFX-O-2 F,SFX-m-2 F,and SFX-p-2 F) endowed with two-armed t rip he ny la mine moieties were synthesized via tuning of the fluorine substitution position,and they were employed for use in highly efficient perovskite solar cells(PSCs).Despite the fluorine substitution position playing a negligible role in the optical and electrochemical properties of the resulting small molecules,the photovoltaic performance thereof was observed to vary significantly.The planar n-i-p PSCs based on SFX-m-2 F demonstrated superior performance(18.86%) when compared to that of the corresponding SFX-o-2 F(9.7%) and SFX-p-2 F(16.33%) under 100 mW cm^(-2) AM1.5 G solar illumination,which is competitive with the performance of the benchmark spiro-OMeTAD-based device(18.98%).Moreover,the SFX-m-2 Fbased PSCs were observed to be more stable than the spiro-OMeTAD-based devices under ambient conditions.The improved performance of SFX-m-2 F is primarily associated with improved morphology,more efficient hole transport,and extraction characteristics at the perovskite/HTM interface.This work demonstrated the application of fluorination engineering to the tuning of material film morphology and charge transfer properties,showing the promising potential of fluorinated SM-HTMs for the construction of low-cost,high-efficiency PSCs.

Thermal-sensitive ionogel with NIR-light controlled adhesion for ultrasoft strain sensor

With the widespread prevailing of flexible electronics in human-machine interfaces,health monitor,and human motion detection,ultrasoft flexible sensors are urgently desired with critical demands in conformality.Herein,a temperature-sensitive ionogel with near-infrared(NIR)-light controlled adhesion is prepared by electrostatic interaction of poly(diallyl dimethylammonium chloride)(PDDA)and acrylic acid,as well as the incorporation of the conductive polydopamine modified polypyrrole nanoparticles(PPy-PDA NPs).The PPy-PDA NPs could weaken the tough interaction between polymer chains and depress the Young’s modulus of the ionogel,thus promoting the ionogel ultrasoft(34 kPa)and highly stretchable(1,013%)performance to tensile deformations.In addition,the high photothermal conversion capacity of PPy-PDA NPs ensured the ionogel excellent NIR-light controlled adhesion and temperature sensitivity,which facilitated the ionogel on-demand removal and promised a reliable thermal sensor.Moreover,the resulted ultrasoft flexible sensor exhibited high sensitivity and stability to both strain and pressure in a broad range of deformations,enabling a precise monitoring on various human motions and physiological activities.The temperature-sensitive,ultrasoft,and controlled adhesive capabilities prompted great potential of the flexible ionogel in medical diagnosis and wearable electronics.

Ultra-thin CoAl layered double hydroxide nanosheets for the construction of highly sensitive and selective QCM humidity sensor

To achieve real-time monitoring of humidity in various applications,we prepared facile and ultra-thin CoAl layered double hydroxide(CoAl LDH)nanosheets to engineer quartz crystal microbalances(QCM).The characteristics of CoAl LDH were investigated by transmission electron microscopy(TEM),X-ray diffraction(XRD),X-ray photoelectric spectroscopy(XPS),Brunauer–Emmett–Telle(BET),atomic force microscopy(AFM)and zeta potential.Due to their large specific surface area and abundant hydroxyl groups,CoAl LDH nanosheets exhibit good humidity sensing performance.In a range of 11.3%and 97.6%relative humidity(RH),the sensor behaved an ultrahigh sensitivity(127.8 Hz/%RH),fast response(9.1 s)and recovery time(3.1 s),low hysteresis(3.1%RH),good linearity(R^(2)=0.9993),stability and selectivity.Besides,the sensor can recover the initial response frequency after being wetted by deionized water,revealing superior self-recovery ability under high humidity.Based on in-situ Fourier transform infrared spectroscopy(FT-IR),the adsorption mechanism of CoAl LDH toward water molecules was explored.The QCM sensor can distinguish different respiratory states of people and wetting degree of fingers,as well as monitor the humidity in vegetable packaging,suggesting excellent properties and a promising application in humidity sensing.