Electro‑copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation

Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.

Alkyl chain modulation of asymmetric hexacyclic fused acceptor synergistically with wide bandgap third component for high efficiency ternary organic solar cells

Herein,two asymmetric hexacyclic fused small molecule acceptors(SMAs),namely BP4F-HU and BP4F-UU,were synthesized.The elongated outside chains in the BP4F-UU molecule played a crucial role in optimizing the morphology of blend film,thereby improving charge mobility and reducing energy loss within the corresponding film.Notably,the PM6:BP4F-UU device exhibited a higher open-circuit voltage(V_(oc))of 0.878 V compared to the PM6:BP4F-HU device with a V_(oc)of 0.863 V.Further,a new wide bandgap SMA named BTP-TA was designed and synthesized as the third component to the PM6:BP4F-UU host binary devices,which showed an ideal complementary absorption spectrum in PM6:BP4F-UU system.In addition,BTP-TA can achieve efficient intermolecular energy transfer to BP4F-UU by fluorescence resonance energy transfer(FRET)pathway,due to the good overlap between the photoluminescence(PL)spectrum of BTP-TA and the absorption region of BP4F-UU.Consequently,ternary devices with 15wt%BTP-TA exhibits broader photon utilization,optimal blend morphology,and reduced charge recombination compared to the corresponding binary devices.Consequently,PM6:BP4F-UU:BTP-TA ternary device achieved an optimal power conversion efficiency(PCE)of 17.83%with simultaneously increased V_(oc)of 0.905 V,short-circuit current density(J_(sc))of 26.14 mA/cm^(2),and fill factor(FF)of 75.38%.

Nitrogen-doping boosts ^(*)CO utilization and H_(2)O activation on copper for improving CO_(2) reduction to C_(2+) products

To improve the electrocatalytic transformation of carbon dioxide (CO_(2)) to multi-carbon (C_(2+)) products is of great importance.Here we developed a nitrogen-doped Cu catalyst,by which the maximum C_(2+) Faradaic efficiency can reach 72.7%in flow-cell system,with the partial current density reaching 0.62 A cm^(-2).The in situ Raman spectra demonstrate that the *CO adsorption can be strengthened on such a N-doped Cu catalyst,thus promoting the *CO utilization in the subsequent C–C coupling step.Simultaneously,the water activation can be well enhanced by N doping on Cu catalyst.Owing to the synergistic effects,the selectivity and activity for C_(2+) products over the N-deoped Cu catalyst are much improved.

Polymer Fiber Rigid Network with High Glass Transition Temperature Reinforces Stability of Organic Photovoltaics

Organic photovoltaics(OPVs)need to overcome limitations such as insufficient thermal stability to be commercialized.The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology,however,exhibiting limited applicability.Therefore,it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor–acceptor compatibilizers,or by introducing another third component.Herein,a unique approach is presented,based on constructing a polymer fiber rigid network with a high glass transition temperature(T_(g))to impede the movement of acceptor and donor molecules,to immobilize the active layer morphology,and thereby to improve thermal stability.A high-T_(g) one-dimensional aramid nanofiber(ANF)is utilized for network construction.Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart.The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart,thereby leaving fundamental processes such as charge separation,transport,and collection,determining the device efficiency,largely unaltered.This strategy is also successfully applied to other photovoltaic systems.The strategy of incorporating a polymer fiber rigid network with high T_(g) offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.

Solution‑Processed Transparent Conducting Electrodes for Flexible Organic Solar Cells with 16.61% Efficiency

Nonfullerene organic solar cells(OSCs)have achieved breakthrough with pushing the efficiency exceeding 17%.While this shed light on OSC commercialization,high-performance flexible OSCs should be pursued through solution manufacturing.Herein,we report a solution-processed flexible OSC based on a transparent conducting PEDOT:PSS anode doped with trifluoromethanesulfonic acid(CF3SO3H).Through a low-concentration and low-temperature CF3SO3H doping,the conducting polymer anodes exhibited a main sheet resistance of 35Ωsq−1(minimum value:32Ωsq−1),a raised work function(≈5.0 eV),a superior wettability,and a high electrical stability.The high work function minimized the energy level mismatch among the anodes,hole-transporting layers and electron-donors of the active layers,thereby leading to an enhanced carrier extraction.The solution-processed flexible OSCs yielded a record-high efficiency of 16.41%(maximum value:16.61%).Besides,the flexible OSCs afforded the 1000 cyclic bending tests at the radius of 1.5 mm and the long-time thermal treatments at 85°C,demonstrating a high flexibility and a good thermal stability.

Optimizing polymer aggregation and blend morphology for boosting the photovoltaic performance of polymer solar cells via a random terpolymerization strategy

Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical structures.In this work,we report two random terpolymer donors(PBNB80 and PBNB50)by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione(NTD)and 1,3-bis(4-chlorothiophen-2-yl)-4 H,8 H-benzo[1,2-c:4,5-c’]dithiophene-4,8-dione(ClBDD),at the same time,the parent polymers(PBNB100 and PBNB00)are also compared to study.These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels.Importantly,aggregation and self-organization properties of the random terpolymer donors are optimized,which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4 Cl.Particularly,a PBNB80:BO-4 Cl blend forms an optimal nanoscale phase-separation morphology,thereby producing an outstanding power conversion efficiency of 16.0%,which is much higher than those(12.8%and 10.7%)of their parent binary polymer donor-based devices.This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.

Ferric acetylacetonate/covalent organic framework composite for high performance photocatalytic oxidation

Ferric acetylacetonate/covalent organic framework(Fe(acac)_(3)/COF)composite was synthesized by interfacial polymerization method at room temperature.The crystal structure,morphology and porosity property of the composite were characterized by X-ray diffraction,scanning electron microscope,transmission electron microscope and nitrogen adsorption.The interaction between Fe(acac)_(3) and COF was investigated by Fourier transform infrared spectra and X-ray photoelectron spectroscopy.The Fe(acac)_(3)/COF composite was used as a photocatalyst for the oxidation of benzyl alcohol under mild conditions.It exhibits high activity and selectivity for the reaction,of which the mechanism was investigated by determining its photoelectric properties.The Fe(acac)_(3)/COF catalyst developed in this work has application potential in other photocatalytic reactions.

Ultra-small UiO-66-NH_(2)nanoparticles immobilized on g-C_(3)N_(4)nanosheets for enhanced catalytic activity

UiO-66-NH_(2),an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It is very meaningful to produce UiO-66-NH_(2) nanoparticles with ultrasmall size,but remains challenging.Herein,we synthesized UiO-66-NH_(2) nanoparticles in size of 8-15 nm that are immobilized on g-C_(3)N_(4)nanosheets.Compared with the UiO-66-NH_(2) synthesized by the traditional solvothermal method(>200 nm),the ultra-small UiO-66-NH_(2) nanoparticles immobilized on g-C_(3)N_(4)have more unsaturated coordination positions and increased Lewis acidity.Owing to these combined advantages,the ultra-small UiO-66-NH_(2)nanoparticles exhibit greatly improved catalytic activity for Meerwein-Ponndorf-Verley reaction than larger UiO-66-NH_(2)particles.

Ultrafast Electron Transfer in All-Small-Molecule Photovoltaic Blends Promoted by Intermolecular Interactions in Cyanided Donors

Cyano substitution has been established as a viable approach to optimize the performance of all-small-molecule organic solar cells.However,the effect of cyano substitution on the dynamics of photo-charge generation remains largely unexplored.Here,we report an ultrafast spectroscopic study showing that electron transfer is markedly promoted by enhanced intermolecular charge-transfer interaction in all-small-molecule blends with cyanided donors.The delocalized excitations,arising from intermolecular interaction in the moiety of cyano-substituted donor,undergo ultrafast electron transfer with a lifetime of∼3 ps in the blend.In contrast,some locally excited states,surviving in the film of donor without cyano substitution,are not actively involved in the charge separation.These findings well explain the performance improvement of devices with cyanided donors,suggesting that manipulating intermolecular interaction is an efficient strategy for device optimization.

Impact of alkyl chain branching positions on molecular packing and electron transport of dimeric perylenediimide derivatives

Side chains play a critical role in tuning intermolecular interaction and charge transport in organic semiconductors. Here, we have systematically investigated the impact of branching positions of the alkyl side chains on the molecular packing and electron transport properties of a series of bay-linked dimeric perylenediimide(PDI) derivatives by atomistic molecular dynamics simulations in combination with charge transfer rate theory and kinetic Monte Carlo simulations. The results show that despite of different branching positions of the alkyl chains,π–π stacking is effectively inhibited for all the dimeric PDI derivatives. As the branching position moves away from the PDI backbone, the appearance of the alkyl atoms around the PDI backbone will first decrease and then increase. Correspondingly, the short contacts between the PDI moieties are first enhanced and then reduced. In particular, when the branching position is at the third carbon atom, the intermolecular connectivity becomes the most effective and the electron mobility is significantly increased by 2 times.

Air-Stable,Eco-Friendly RRAMs Based on Lead-Free Cs_(3)Bi_(2)Br_(9)Perovskite Quantum Dots for High-Performance Information Storage

Development of lead-free halide perovskites that are innocuous and stable has become an attractive trend in resistive random access memory(RRAM)fields.However,their inferior memory properties compared with the lead-based analogs hinder their commercialization.Herein,the lead-free Cs_(3)Bi_(2)Br_(9)perovskite quantum dot(PQD)-based RRAMs are reported with outstanding memory performance,where Cs_(3)Bi_(2)Br_(9)quantum dots(QDs)are synthesized via a modified ligand-assisted recrystallization process.This is the first report of applying Cs_(3)Bi_(2)Br_(9)QDs as the switching layer for RRAM device.The Cs_(3)Bi_(2)Br_(9)QD device demonstrates nonvolatile resistive switching(RS)effect with large ON/OFF ratio of 105,low set voltage of-0.45 V,as well as good reliability,reproducibility,and flexibility.Concurrently,the device exhibits the notable tolerance toward moisture,heat and light illumination,and long-term stability of 200 days.More impressively,the device shows the reliable light-modulated RS behavior,and therefrom the logic gate operations including"AND"and"OR"are implemented,foreboding its prospect in logic circuits integrated with storage and computation.Such multifunctionality of device could be derived from the unique 2D layered crystal structure,small particle size,quantum confinement effect,and photoresponse of Cs_(3)Bi_(2)Br_(9)QDs.This work provides the strategy toward the high-performance RRAMs based on stable and eco-friendly perovskites for future applications.

Prolonging charge carrier lifetime via reinforcing molecular stacking for high-efficiency organic solar cells

Limited charge carrier lifetime(τ)leads to the short charge carrier diffusion length(L_(D))and thus impedes the improvement of power conversion efficiencies(PCEs)of organic solar cells(OSCs).Herein,anthracene(AN)as the additive is introduced into classical donor:acceptor pairs to increase theτ.Introducing AN efficiently enhances the crystallinity of the PM 6:BTP-eC 9+blend film to reduce the trap density and increase theτto 1.484μs,achieving the prolonged L_(D).The prolonged L_(D) enables the PM 6:BTP-eC 9+blend film to gain weaker charge carrier recombination,reduced leakage current,and shorter charge carrier extraction time in devices,compared with PM 6:BTP-eC 9 counterparts.Therefore,PM 6:BTP-eC 9+based OSCs achieve higher PCEs of 18.41%±0.16%than PM 6:BTP-eC 9 based ones(17.08%±0.11%).Moreover,the PM 6:L 8-BO+based OSC presents an impressive PCE of 19.14%.It demonstrates that introducing AN is an efficient method to increase theτfor prolonged L_(D),boosting PCEs of OSCs.

The critical role of energetic fluctuations in charge separation for efficient molecular doping of organic semiconductors

Molecular doping is essential to improve the electrical conductivity of organic semiconductors for high-performance organic electronic devices. However, the doping efficiency is influenced by several factors, such as the energy levels, energetic fluctuations, dielectric properties, and molecular packing structures of the doped films, and the underlying mechanisms for highefficiency doping are still unclear. Here, through multi-level theoretical simulations on a series of fullerene derivatives, we identify that the energetic fluctuations can play a decisive role in activating charge separation for molecular doping. In particular,the doping efficiency appears to be exponentially increased with the fluctuation of charge polarization energies. Therefore,although the charge mobility is somewhat decreased, the experimental electrical conductivity is improved with the increased energetic fluctuation. Moreover, it has been found that polarization energy fluctuation can be effectively enhanced by simply introducing side chains with greater flexibility into organic semiconductors. This article paves the way towards high-efficiency molecular doping of organic semiconductors.

Semitransparent organic photovoltaics enabled by transparent p-type inorganic semiconductor and near-infrared acceptor

Semitransparent organic photovoltaics(STOPVs)have gained wide attention owing to their promising applications in building-integrated photovoltaics,agrivoltaics,and floating photovoltaics.Organic semiconductors with high charge carrier mobility usually have planar and conjugated structures,thereby showing strong absorption in visible region.In this work,a new concept of incorporating transparent inorganic semiconductors is proposed for high-performance STOPVs.Copper(I)thiocyanate(CuSCN)is a visible-transparent inorganic semiconductor with an ionization potential of 5.45 eV and high hole mobility.The transparency of CuSCN benefits high average visible transmittance(AVT)of STOPVs.The energy levels of CuSCN as donor match those of near-infrared small molecule acceptor BTP-eC9,and the formed heterojunction exhibits an ability of exciton dissociation.High mobility of CuSCN contributes to a more favorable charge transport channel and suppresses charge recombination.The control STOPVs based on PM6/BTP-eC9 exhibit an AVT of 19.0%with a power conversion efficiency(PCE)of 12.7%.Partial replacement of PM6 with CuSCN leads to a 63%increase in transmittance,resulting in a higher AVT of 30.9%and a comparable PCE of 10.8%.

π-Bridge mediated coupling between inter-and intra-molecular charge transfer in aggregates for highly efficient near-infrared emission

Intermolecular charge transfer(inter-CT)is commonly considered to quench luminescence in molecular aggregates,especially for near-infrared(NIR)emission.Herein,by elaborate comparison ofπ-bridge effects in donor/acceptor(D/A)molecules,it is disclosed that aπ-bridge is essential in D/A molecule to involve inter-CT in aggregates for inducing desired thermally activated delayed fluorescence(TADF)and largely suppressing non-radiative decays,and importantly,electrondonatingπ-bridge is critical to maximize radiative decay for inter-CT dominated emission by effective electronic coupling with bright intramolecular charge transfer(intra-CT)for high-efficiency NIR emission.As a proof-of-concept,TPATAP with thienyl asπ-bridge realized prominent photoluminescence quantum yields of 18.9%at 788 nm in solid films,and achieved record-high maximum external quantum efficiencies of 4.53%at 785 nm in devices.These findings provide fresh insight into interplay between inter-CT and intra-CT in molecular aggregates and open a new avenue to attenuate the limitation of energy gap law for developing highly efficient NIR emitters and improving the luminescent efficiency of various inter-CT systems,such as organic photovoltaic,organic long persistent luminescence,etc.

Efficient electrocatalytic reduction of carbon dioxide to ethylene on copper–antimony bimetallic alloy catalyst

The exploration of efficient electrocatalysts for the reduction of CO2 to C2H4 is of significant importance but is also a challenging subject.Cu-based bimetallic catalysts are extremely promising for efficient CO2 reduction.In this work,we synthesize a series of porous bimetallic Cu–Sb alloys with different compositions for the catalytic reduction of CO2 to C2H4.It is demonstrated that the alloy catalysts are much more efficient than the pure Cu catalyst.The performance of the alloy catalysts depended strongly on the composition.Further,the alloy with a Cu:Sb ratio of 10:1 yielded the best results;it exhibited a high C2H4 Faradaic efficiency of 49.7%and a high current density of 28.5 mA cm?2 at?1.19 V vs.a reversible hydrogen electrode(RHE)in 0.1 M KCl solution.To the best of our knowledge,the electrocatalytic reduction of CO2 to C2H4 using Cu–Sb alloys as catalysts has not been reported.The excellent performance of the porous alloy catalyst is attributed to its favorable electronic configuration,large surface area,high CO2 adsorption rate,and fast charge transfer rate.

Fluorination vs. chlorination： a case study on high performance organic photovoltaic materials

Halogenation is a very efficient chemical modification method to tune the molecular energy levels, absorption spectra and molecular packing of organic semiconductors. Recently, in the field of organic solar cells(OSCs), both fluorine-and chlorinesubstituted photovoltaic materials, including donors and acceptors, demonstrated their great potentials in achieving high power conversion efficiencies(PCEs), raising a question that how to make a decision between fluorination and chlorination when designing materials. Herein, we systemically studied the impact of fluorination and chlorination on the properties of resulting donors(PBDB-T-2 F and PBDB-T-2 Cl) and acceptors(IT-4 F and IT-4 Cl). The results suggest that all the OSCs based on different donor and acceptor combinations can deliver good PCEs around 13%–14%. Chlorination is more effective than fluorination in downshifting the molecular energy levels and broadening the absorption spectra. The influence of chlorination and fluorination on the crystallinity of the resulting materials is dependent on their introduction positions. As chlorination has the advantage of easy synthesis, it is more attractive in designing low-cost photovoltaic materials and therefore may have more potential in largescale applications.

Enhanced CO_(2)electroreduction to ethylene via strong metal-support interaction

The CuO/CeO_(2) composites with strong metal-support interaction were synthesised,which can efficiently electroreduct CO_(2)to C(2)H_(4).The Faradaic efficiency(FE)of C_(2)H_(4) could reach 50.5%with a current density of 18 mA cm^(-2).The strong metal-support interaction could not only enhance the adsorption and activation of CO_(2),but also can stablize the CuO.

Controllable oxygen vacancies and morphology engineering:Ultra-high HER/OER activity under base–acid conditions and outstanding antibacterial properties

Introducing vacancy defects and unique morphology is an effective strategy to improve the catalytic performance of transition metal compounds.However,precisely controlling the amount of vacancy defects remains challenging.Here,we propose a facile and efficient hydrothermal accompanying an annealing method to synthesize a series of Mn-doped CoO nanomaterials with controllable oxygen vacancies and unique morphology.The oxygen vacancies amount can be precisely controlled by adjusting the Mndoping content and is positively correlated with catalytic performance.It was found that the oxygen vacancies amount can reach up to 38.2%over the Mn-doped CoO nanomaterials,resulting in ultra-high hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalytic activity(HER:25.6 and 37 m V at 10 m A cm^(-2);OER:301 and 322 m V at 50 m A cm^(-2))under both basic and acidic conditions,while reaching 10 m A cm^(-2) for an ultra-low cell voltage of only 1.52 V,which exceeds that of Pt/C/RuO_(2) and all reported non-noble metal oxide catalysts.The DFT calculations reveal oxygen vacancies can optimize H*and HOO*intermediates adsorption free energy,thus improving the HER and OER performance.Interestingly,the Mn-doped CoO with rich oxygen vacancies exhibits excellent antibacterial properties in vitro of biomedicine.This work provides new ideas and methods for the rational design and precise control of vacancy defects in transition metal compounds and explores their potential application value in electrochemical water splitting and biomedical fields.

Insights into the nitride-regulated processes at the electrolyte/electrode interface in quasi-solid-state lithium metal batteries

Gel polymer electrolytes(GPEs)are one of the promising candidates for high-energy-density quasi-solid-state lithium metal batteries(QSSLMBs),for their high ionic conductivity and excellent interfacial compatibility.The comprehension of dynamic evolution and structure-reactivity correlation at the GPE/Li interface becomes significant.Here,in situ electrochemical atomic force microscopy(EC-AFM)provides insights into the LiNO_(3)-regulated micromechanism of the Li plating/stripping processes upon cycles in GPE-based LMBs at nanoscale.The additive LiNO_(3)induces the formation of amorphous nitride SEI film and facilitates Li^(+) ion diffusion.It stabilizes a compatible interface and regulates the Li nucleation/growth at steady kinetics.The deposited Li is in the shape of chunks and tightly compact.The Li dissolution shows favorable reversibility,which guarantees the cycling performance of LMBs.In situ AFM monitoring provides a deep understanding into the dynamic evolution of Li deposition/dissolution and the interphasial properties of tunable SEI film,regulating the rational design of electrolyte and optimizing interfacial establishment for GPE-based QSSLMBs.