Fabrication of Organic/Polymeric Superlattice Structure and Its Use for Electroluminescent Device

Superlattices consisting of alternating layers of organic/polymeric materials have been fabricated from tris(8-hydroxyquinoline)aluminum(Alq3) and poly(N-vinylcarbazole)(PVK) by a multisource-type high-vacuum organic molecular deposition.The characteristics of superlattice structures are determined by the small-angle X-ray diffraction,optical absorption and photoluminescence.The electroluminescent devices with the superlattice structure have also been fabricated and the emission characteristics are discussed.

Ultraviolet‑Irradiated All‑Organic Nanocomposites with Polymer Dots for High‑Temperature Capacitive Energy Storage

Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.

Metal-Organic Framework Enabling Poly(Vinylidene Fluoride)-Based Polymer Electrolyte for Dendrite-Free and Long-Lifespan Sodium Metal Batteries

Sodium dentrite formed by uneven plating/stripping can reduce the utilization of active sodium with poor cyclic stability and,more importantly,cause internal short circuit and lead to thermal runaway and fire.Therefore,sodium dendrites and their related problems seriously hinder the practical application of sodium metal batteries(SMBs).Herein,a design concept for the incorporation of metal-organic framework(MOF)in polymer matrix(polyvinylidene fluoride-hexafluoropropylene)is practiced to prepare a novel gel polymer electrolyte(PH@MOF polymer-based electrolyte[GPE])and thus to achieve high-performance SMBs.The addition of the MOF particles can not only reduce the movement hindrance of polymer chains to promote the transfer of Na^(+)but also anchor anions by virtue of their negative charge to reduce polarization during electrochemical reaction.A stable cycling performance with tiny overpotential for over 800 h at a current density of 5 mA cm^(-2)with areal capacity of 5 mA h cm^(-2)is achieved by symmetric cells based on the resulted GPE while the Na_(3)V_(2)O_(2)(PO_(4))_(2)F@rGO(NVOPF)|PH@MOF|Nacell also displays impressive specific cycling capacity(113.3 mA h g^(-1)at 1 C)and rate capability with considerable capacity retention.

A novel metal-free porous covalent organic polymer for efficient room-temperature photocatalytic CO_(2) reduction via dry-reforming of methane

At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.

Achieving Synergistic Improvement in Dielectric and Energy Storage Properties of All-Organic Poly(Methyl Methacrylate)-Based Copolymers Via Establishing Charge Traps

How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.

Organic X-Ray Image Sensors Using a Medium Bandgap Polymer Donor with Low Dark Current

The development of portable X-ray detectors is necessary for diagnosing fractures in unconscious patients in emergency situations.However,this is quite challenging because of the heavy weight of the scintillator and silicon photodetectors.The weight and thickness of X-ray detectors can be reduced by replacing the silicon layer with an organic photodetectors.This study presents a novel bithienopyrroledione-based polymer donor that exhibits excellent photodetection properties even in a thick photoactive layer(~700 nm),owing to the symmetric backbone and highly soluble molecular structure of bithienopyrroledione.The ability of bithienopyrroledione-based polymer donor to strongly suppress the dark current density(Jd~10−10 A cm^(−2))at a negative bias(−2.0 V)while maintaining high responsivity(R=0.29 A W−1)even at a thickness of 700 nm results in a maximum shot-noise-limited specific detectivity of D_(sh)^(*)=2.18×10^(13)Jones in the organic photodetectors.Printed organic photodetectors are developed by slot-die coating for use in X-ray detectors,which exhibit D_(sh)^(*)=2.73×10^(12)Jones with clear rising(0.26 s)and falling(0.29 s)response times upon X-ray irradiation.Detection reliability is also proven by linear response of the X-ray detector,and the X-ray detection limit is 3 mA.

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.

Impact of transparent exopolymer particles on the dynamics of dissolved organic carbon in the Amundsen Sea,Antarctica

The Southern Ocean is an important carbon sink pool and plays a critical role in the global carbon cycling.The Amundsen Sea was reported to be highly productive in inshore area in the Southern Ocean.In order to investigate the influence of transparent exopolymer particles(TEP)on the behavior of dissolved organic carbon(DOC)in this region,a comprehensive study was conducted,encompassing both open water areas and highly productive polynyas.It was found that microbial heterotrophic metabolism is the primary process responsible for the production of humic-like fluorescent components in the open ocean.The relationship between apparent oxygen utilization and the two humic-like components can be accurately described by a power-law function,with a conversion rate consistent with that observed globally.The presence of TEP was found to have little impact on this process.Additionally,the study revealed the accumulation of DOC at the sea surface in the Amundsen Sea Polynya,suggesting that TEP may play a critical role in this phenomenon.These findings contribute to a deeper understanding of the dynamics and surface accumulation of DOC in the Amundsen Sea Polynya,and provide valuable insights into the carbon cycle in this region.

Heavy metal complex containing organic/polymer materials for bulk-heterojunction photovoltaic devices

The application of heavy-metal complexes in bulk-heterojunction（BHJ） solar cells is a promising new research field which has attracted increasing attention,due to their strong spin-orbit coupling for efficient singlet to triplet intersystem crossing.This review article focuses on recent advances of heavy metal complex containing organic and polymer materials as photovoltaic donors in BHJ solar cells.Platinum-acetylide containing oligomersor and polymers have been firstly illustrated due to the good solubility,square planar structure,as well as the fairly strong Pt-Pt interaction.Then the cyclometalated Pt or Ir complex containing conjugated oligomers and polymers are presented in which the triplet organometallic compounds are embedded into the organic/polymer backbone either through cyclometalated main ligand or the auxiliary ligand.Pure triplet small molecular cyclometalated Ir complex are also briefly introduced.Besides the chemical modification,physical doping of cyclometalated heavy metal complexes as additives into the photovoltaic active layers is finally demonstrated.

Molecular Structure Tailoring of Organic Spacers for High‑Performance Ruddlesden–Popper Perovskite Solar Cells

Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(PSC)technology.However,two-dimensional(2D)or quasi-2D RP PSCs are encountered with some challenges of the large exciton binding energy,blocked charge transport and poor film quality,which restrict their photovoltaic performance.Fortunately,these issues can be readily resolved by rationally designing spacer cations of RPPs.This review mainly focuses on how to design the molecular structures of organic spacers and aims to endow RPPs with outstanding photovoltaic applications.We firstly elucidated the important roles of organic spacers in impacting crystallization kinetics,charge transporting ability and stability of RPPs.Then we brought three aspects to attention for designing organic spacers.Finally,we presented the specific molecular structure design strategies for organic spacers of RPPs aiming to improve photovoltaic performance of RP PSCs.These proposed strategies in this review will provide new avenues to develop novel organic spacers for RPPs and advance the development of RPP photovoltaic technology for future applications.

Porous Organic Cage‑Based Quasi‑Solid‑State Electrolyte with Cavity‑Induced Anion‑Trapping Effect for Long‑Life Lithium Metal Batteries

Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.

Bioinspired Passive Tactile Sensors Enabled by Reversible Polarization of Conjugated Polymers

Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.

An Unprecedented Efficiency with Approaching 21%Enabled by Additive‑Assisted Layer‑by‑Layer Processing in Organic Solar Cells

Recently published in Joule,Feng Liu and colleagues from Shanghai Jiaotong University reported a record-breaking 20.8%power conversion efficiency in organic solar cells(OSCs)with an interpenetrating fibril network active layer morphology,featuring a bulk p-in structure and proper vertical segregation achieved through additive-assisted layer-by-layer deposition.This optimized hierarchical gradient fibrillar morphology and optical management synergistically facilitates exciton diffusion,reduces recombination losses,and enhances light capture capability.This approach not only offers a solution to achieving high-efficiency devices but also demonstrates the potential for commercial applications of OSCs.

Merging polymers of intrinsic microporosity and porous carbon-based zinc oxide composites in novel mixed matrix membranes for efficient gas separation

Mixed matrix membranes(MMMs)have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers.However,achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge,due to the difficulty of achieving an optimal match between polymers and fillers.In this study,we incorporate a porous carbon-based zinc oxide composite(C@ZnO)into high-permeability polymers of intrinsic microporosity(PIMs)to fabricate MMMs.The dipole–dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility,mitigating the formation of non-selective voids in the resulting MMMs.Concurrently,C@ZnO with abundant interconnected pores can provide additional low-resistance pathways for gas transport in MMMs.As a result,the CO_(2) permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13,215 barrer,while the CO_(2)/N_(2) and CO_(2)/CH_(4) selectivity reached 21.5 and 14.4,respectively,substantially surpassing the 2008 Robeson upper bound.Additionally,molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO_(2) affinity of C@ZnO.In summary,we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.

A Pd-metalated porous organic polymer as a highly efficient heterogeneous catalyst for C–C couplings

An efficient catalyst system based on a Pd-metalated porous organic polymer bearing phenanthroline ligands was designed and synthesized.This catalyst was applied to various C–C bond-forming reactions,including the Suzuki,Heck and Sonogashira couplings,and afforded the corresponding products while exhibiting excellent activities and selectivities.More importantly,this catalyst can be readily recycled.These features show that such catalysts have significant potential applications in the future.

Organic fertilizer enhances soil aggregate stability by altering greenhouse soil content of iron oxide and organic carbon

Both soil organic carbon (SOC) and iron (Fe) oxide content, among other factors, drive the formation and stability of soil aggregates.However, the mechanism of these drivers in greenhouse soil fertilized with organic fertilizer is not well understood.In a 3-year field experiment, we aimed to investigate the factors which drive the stability of soil aggregates in greenhouse soil.To explore the impact of organic fertilizer on soil aggregates, we established four treatments:no fertilization (CK);inorganic fertilizer (CF);organic fertilizer (OF);and combined application of inorganic and organic fertilizers(COF).The application of organic fertilizer significantly enhanced the stability of aggregates, that is it enhanced the mean weight diameter, geometric mean diameter and aggregate content (%) of>0.25 mm aggregate fractions.OF and COF treatments increased the concentration of SOC, especially the aliphatic-C, aromatic-C and polysaccharide-C components of SOC, particularly in>0.25 mm aggregates.Organic fertilizer application significantly increased the content of free Fe(Fed), reactive Fe (Feo), and non-crystalline Fe in both bulk soil and aggregates.Furthermore, non-crystalline Fe showed a positive correlation with SOC content in both bulk soil and aggregates.Both non-crystalline Fe and SOC were significantly positively correlated with>2 mm mean weight diameter.Overall, we believe that the increase of SOC, aromatic-C, and non-crystal ine Fe concentrations in soil after the application of organic fertilizer is the reason for improving soil aggregate stability.

Neurotransmitter-mediated artificial synapses based on organic electrochemical transistors for future biomimic and bioinspired neuromorphic systems

Organic electrochemical transistors have emerged as a solution for artificial synapses that mimic the neural functions of the brain structure,holding great potentials to break the bottleneck of von Neumann architectures.However,current artificial synapses rely primarily on electrical signals,and little attention has been paid to the vital role of neurotransmitter-mediated artificial synapses.Dopamine is a key neurotransmitter associated with emotion regulation and cognitive processes that needs to be monitored in real time to advance the development of disease diagnostics and neuroscience.To provide insights into the development of artificial synapses with neurotransmitter involvement,this review proposes three steps towards future biomimic and bioinspired neuromorphic systems.We first summarize OECT-based dopamine detection devices,and then review advances in neurotransmitter-mediated artificial synapses and resultant advanced neuromorphic systems.Finally,by exploring the challenges and opportunities related to such neuromorphic systems,we provide a perspective on the future development of biomimetic and bioinspired neuromorphic systems.

Long-term combined application of organic and inorganic fertilizers increases crop yield sustainability by improving soil fertility in maize-wheat cropping systems

Organic material combined with inorganic fertilizer has been shown to greatly improve crop yield and maintain soil fertility globally. However, it remains unclear if crop yield and soil fertility can be sustained in the long term under the combined application of organic and inorganic fertilizers. Three long-term field trials were conducted to investigate the effects of organic amendments on the grain sustainable yield index(SYI), soil fertility index(SFI)and nutrient balance in maize–wheat cropping systems of central and southern China during 1991–2019. Five treatments were included in the trials: 1) no fertilization(control);2) balanced mineral fertilization(NPK);3) NPK plus manure(NPKM);4) high dose of NPK plus manure(1.5NPKM);and 5) NPK plus crop straw(NPKS). Over time, the grain yields of wheat and maize showed an increasing trend in all four fertilization treatments at the Yangling(YL) and Zhengzhou(ZZ) locations, while they declined at Qiyang(QY). The grain yield in the NPKM and 1.5NPKM treatments gradually exceeded that of the NPK and NPKS treatments at the QY site. The largest SYI was recorded in the NPKM treatment across the three sites, suggesting that inorganic fertilizer combined with manure can effectively improve crop yield sustainability. Higher SYI values were recorded at the YL and ZZ sites than at the QY site, possibly because the soil was more acid at QY. The key factors affecting grain yield were soil available phosphorus(AP) and available potassium(AK) at the YL and ZZ sites, and pH and AP at the QY site.All fertilization treatments resulted in soil N and P surpluses at the three sites, but soil K surpluses were recorded only at the QY site. The SFI was greater in the 1.5NPKM, NPKM and NPKS treatments than in the NPK treatment by 13.3–40.0 and 16.4–63.6% at the YL and ZZ sites, respectively, and was significantly higher in the NPKM and 1.5NPKM treatments than in the NPK and NPKS treatments at the QY site. A significant, positive linear relationship was found between SFI and crop yield, and SYI and nutrient balance, indicating that grain yield and its sustainability significantly increased with increasing soil fertility. The apparent N, P and K balances positively affected SFI.This study suggests that the appropriate amount of manure mixed with mineral NPK fertilizer is beneficial to the development of sustainable agriculture, which effectively increases the crop yield and yield sustainability by improving soil fertility.

A novel nano-grade organosilicon polymer:Improving airtightness of compressed air energy storage in hard rock formations

Enhancing cavern sealing is crucial for improving the efficiency of compressed air energy storage(CAES)in hard rock formations.This study introduced a novel approach using a nano-grade organosilicon polymer(NOSP)as a sealant,coupled with an air seepage evaluation model that incorporates Knudsen diffusion.Moreover,the initial coating application methods were outlined,and the advantages of using NOSP compared to other sealing materials,particularly regarding cost and construction techniques,were also examined and discussed.Experimental results indicated a significant reduction in permeability of rock specimens coated with a 7–10μm thick NOSP layer.Specifically,under a 0.5 MPa pulse pressure,the permeability decreased to less than 1 n D,and under a 4 MPa pulse pressure,it ranged between4.5×10^(-6)–5.5×10^(-6)m D,marking a 75%–80%decrease in granite permeability.The sealing efficacy of NOSP surpasses concrete and is comparable to rubber materials.The optimal viscosity for application lies between 95 and 105 KU,and the coating thickness should ideally range from 7 to 10μm,applied to substrates with less than 3%porosity.This study provides new insights into air transport and sealing mechanisms at the pore level,proposing NOSP as a cost-effective and simplified solution for CAES applications.

Preparation and characterization of organic polymer modified composite polyaluminum chloride

Compared with traditional aluminum salts, polyaluminum chloride （PACI） has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging function. In order to improve the aggregating property of PACl, different composite PACl flocculants were prepared with various organic polymers. The effect of organic polymer on the distribution or Al（Ⅲ） species in composite flocculants was studied using ^27TAl NMR and Al-ferron complexation methods. The charge neutralization and surface adsorption characteristics of composite flocculants were also investigated. Jar tests were conducted to evaluate the turbidity removal efficacy of organic polymer modified composite flocculants. The study shows that cationic polymer and anionic polymer have significant influences on the coagulation-flocculation behaviors of PACl. Both cationic and anionic polymers can improve the turbidity removal performancc of PACl but the mechanisms arc much different： cationic organic polymer mainly increases the charge neutralization ability, but anionic polymer mainly enhances the bridging function.