Flexible and Robust Core-Shell PANI/PVDF@PANI Nanofiber Membrane for High-Performance Electromagnetic Interference Shielding.

Developing high-performance electromagnetic interference (EMI) shielding materials that are lightweight and flexible and have excellent mechanical properties is an ideal choice for modern integrated electronic devices and microwave protection. Herein, we report the preparation of core-shell polyaniline (PANI)-based nanofiber membranes for EMI shielding through seed polymerization. Electrospinning a PANI solution leads to homogeneously dispersed PANI on the nanofiber surface, with abundant attachment sites for aniline through electrostatic adsorption and hydrogen bonding interaction, allowing PANI to grow on the nanofiber surfaces. This stable core-shell heterostructure provides more interfaces for reflecting and absorbing microwaves. The PANI/PVDF@PANI membranes achieved a shielding efficiency (SE) of 44.7 dB at a thickness of only 1.2 mm, exhibiting an exceptionally high specific EMI shielding effectiveness (SE/t) of 372.5 dB cm-1. Furthermore, the composite membrane exhibits outstanding mechanical stability, durability, air permeability, and moisture permeability, also making it suitable for applications such as EM shielding clothing.

Synthesis of Metal-Nitrogen-Carbon Electrocatalysts with Atomically Regulated Nitrogen-Doped Polycyclic Aromatic Hydrocarbons.

Tuning the active site structure of metal-nitrogen-carbon electrocatalysts has recently attracted increasing interest. Herein, we report a bottom-up synthesis strategy in which atomically regulated N-doped polycyclic aromatic hydrocarbons (N-PAHs) of NxC42-x (x = 1, 2, 3, 4) were used as ligands to allow tuning of the active site's structures of M-Nx and establish correlations between the structures and electrocatalytic properties. Based on the synthesis process, detailed characterization, and DFT calculation results, active structures of Nx-Fe1-Nx in Fe1-Nx/RGO catalysts were constructed. The results demonstrated that the extra uncoordinated N atoms around the Fe1-N4 moieties disrupted the π-conjugated NxC42-x ligands, which led to more localized electronic state in the Fe1-N4 moieties and superior catalytic performance. Especially, the Fe1-N4/RGO exhibited optimized performance for ORR with E1/2 increasing by 80 mV and Jk at 0.85 V improved 18 times (compared with Fe1-N1/RGO). This synthesis strategy utilizing N-PAHs holds significant promise for enhancing the controllability of metal-nitrogen-carbon electrocatalyst preparation.

Tailoring Zirconia Supported Intermetallic Platinum Alloy via Reactive Metal-Support Interactions for High-Performing Fuel Cells.

Developing efficient and anti-corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal-support interaction (RMSI) as ORR catalysts, using Ni-doped cubic ZrO2 (Ni/ZrO2) supported L10-PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentrations in the support are increased, leading to an electron enrichment of Pt. The optimal L10-PtNi-Ni/ZrO2-RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8 %) after 400,000 accelerated durability test cycles in a half-cell and exceptional PEMFC performance (MA=0.76 A mgPt -1 at 0.9 V, peak power density=1.52/0.92 W cm-2 in H2-O2/-air, and 18.4 % MA decay after 30,000 cycles), representing the best reported Pt-based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L10-PtNi-Ni/ZrO2-RMSI requires a lower energetic barrier for ORR than L10-PtNi-Ni/ZrO2 (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L10-PtNi-Ni/ZrO2-RMSI compared to L10-PtNi-C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy.

Tuning an Electrode Work Function Using Organometallic Complexes in Inverted Perovskite Solar Cells.

Low-work-function (WF) metals (including silver (Ag), aluminum (Al), and copper (Cu)) used as external cathodes in inverted perovskite solar cells (PSCs) encounter oxidation caused by air exposure and halogen-diffusion-induced corrosion, which threaten the long-term stability of the device. The cathode interlayer (CIL) has shown promise in reducing the metal WF and thus boosting the device power conversion efficiency (PCE). However, it remains a challenge for current CIL materials to enable high-WF metals (e.g., Au) to be used as cathodes to achieve PSCs with a superior PCE and long-term stability. Here, we use a series of synthesized (carbolong-derived) organometallic complexes as CILs to tune the electrode WF in inverted PSCs. Density functional theory calculations and surface characterizations show that the organometallic complexes that contain anions and cations are prone to form anion-cation dipoles on the metal surface, hence drastically reducing the metal's WF. Photovoltaic devices based on a Ag cathode, which was modified with these organometallic complexes, received a boosted PCE up to 21.29% and a remarkable fill factor that reached 83.52%, which are attributed to the dipole-enhanced carrier transport. The environmental stability of PSCs was further improved after employing Au as a cathode with these organometallic complexes, and the modified devices exhibited no efficiency loss after 4080 h storage measurements.

Constructing Co-N-C Catalyst via a Double Crosslinking Hydrogel Strategy for Enhanced Oxygen Reduction Catalysis in Fuel Cells.

Exploiting platinum-group-metal (PGM)-free electrocatalysts with remarkable activity and stability toward oxygen reduction reaction (ORR) is of significant importance to the large-scale commercialization of proton exchange membrane fuel cells (PEMFCs). Here, a high-performance and anti-Fenton reaction cobalt-nitrogen-carbon (Co-N-C) catalyst is reported via employing double crosslinking (DC) hydrogel strategy, which consists of the chemical crosslinking between acrylic acid (AA) and acrylamide (AM) copolymerization and metal coordinated crosslinking between Co2+ and P(AA-AM) copolymer. The resultant DC hydrogel can benefit the Co2+ dispersion via chelated Co-N/O bonds and relieve metal agglomeration during the subsequent pyrolysis, resulting in the atomically dispersed Co-Nx/C active sites. By optimizing the ratio of AA/AM, the optimal P(AA-AM)(5-1)-Co-N catalyst exhibits a high content of nitrogen doping (12.36 at%) and specific surface area (1397 m2 g-1 ), significantly larger than that of the PAA-Co-N catalyst (10.59 at%/746 m2 g-1 ) derived from single crosslinking (SC) hydrogel. The electrochemical measurements reveal that P(AA-AM)(5-1)-Co-N possesses enhanced ORR activity (half-wave potential (E1/2 ) ≈0.820 V versus the reversible hydrogen electrode (RHE)) and stability (≈4 mV shift in E1/2 after 5000 potential cycles in 0.5 m H2 SO4 at 60 ºC) relative to PAA-Co-N, which is higher than most Co-N-C catalysts reported so far.

Evidence for Ferroelectricity of All-Inorganic Perovskite CsPbBr3 Quantum Dots.

The combination of ferroelectric-optical properties in halide perovskites has attracted tremendous interess because of its potential for optoelectronic and energy applications. However, very few reports focus on the ferroelectricity of all-inorganic halide perovskites quantum dots. Herein, we report a excellent ferroelectricity in CsPbBr3 quantum dots (QDs) with a saturation polarization of 0.25 µC/cm2. Differential scanning calorimetry, X-ray diffraction, and transmission electronic microscopy revealed that the mechanism of ferroelectric-paraelectric switching of CsPbBr3 QDs can be attributed to the phase transition from cubic phase (Pm3̅m) to the orthorhombic phase (Pna21). In the orthorhombic CsPbBr3, the distortion of octahedral [PbBr6]4- structural units and the off-center Cs+ generated the slightly separated centers of positive charge and negative charge, resulting in the ferroelectric properties. The variable-temperature emission spectrum from 328 to 78 K exhibits green luminescence and a gradual red shift due to the phase transition. This finding opens up an avenue to explore the ferroelectric-optical properties of inorganolead halide perovskites for high-performance multifunctional materials.

Unraveling the Raman Enhancement Mechanism on 1T'-Phase ReS2 Nanosheets.

2D transition metal dichalcogenides materials are explored as potential surface-enhanced Raman spectroscopy substrates. Herein, a systematic study of the Raman enhancement mechanism on distorted 1T (1T') rhenium disulfide (ReS2 ) nanosheets is demonstrated. Combined Raman and photoluminescence studies with the introduction of an Al2 O3 dielectric layer unambiguously reveal that Raman enhancement on ReS2 materials is from a charge transfer process rather than from an energy transfer process, and Raman enhancement is inversely proportional while the photoluminescence quenching effect is proportional to the layer number (thickness) of ReS2 nanosheets. On monolayer ReS2 film, a strong resonance-enhanced Raman scattering effect dependent on the laser excitation energy is detected, and a detection limit as low as 10-9 m can be reached from the studied dye molecules such as rhodamine 6G and methylene blue. Such a high enhancement factor achieved through enhanced charge interaction between target molecule and substrate suggests that with careful consideration of the layer-number-dependent feature and excitation-energy-related resonance effect, ReS2 is a promising Raman enhancement platform for sensing applications.

Conjugation of Amphiphilic Proteins to Hydrophobic Ligands in Organic Solvent.

Protein-ligand conjugations are usually carried out in aqueous media in order to mimic the environment within which the conjugates will be used. In this work, we focus on the conjugation of amphiphilic variants of elastin-like polypeptide (ELP), short elastin (sEL), to poorly water-soluble compounds like OPPVs ( p-phenylenevinylene oligomers), triarylamines, and polypyridine-metal complexes. These conjugations are problematic when carried out in aqueous phase because hydrophobic ligands tend to avoid exposure to water, which in turn causes the ligand to self-aggregate and/or interact noncovalently with hydrophobic regions of the amphiphile. Ultimately, this behavior leads to low conjugation efficiency and contamination with strong noncovalent "conjugates". After exploring the solubility of sEL in various organic solvents, we have established an efficient conjugation methodology for obtaining covalent conjugates virtually free of contaminating noncovalent complexes. When conjugating carboxylated ligands to the amphiphile amines, we demonstrate that even when only one amine (the N-terminus) is present, its derivatization is 98% efficient. When conjugating amine moieties to the amphiphile carboxyls (a problematic configuration), protein multimerization is avoided, 98-100% of the protein is conjugated, and the unreacted ligand is recovered in pure form. Our syntheses occur in "one pot", and our purification procedure is a simple workup utilizing a combination of water and organic solvent extractions. This conjugation methodology might provide a solution to problems arising from solubility mismatch of protein and ligand, and it is likely to be widely applied for modification of recombinant amphiphiles used for drug delivery (PEG-antibodies, polymer-enzymes, food proteins), cell adhesion (collagen, hydrophobins), synthesis of nanostructures (peptides), and engineering of biocompatible optoelectronics (biological polymers), to cite a few.

Towards high-efficiency nanoelectrocatalysts for oxygen reduction through engineering advanced carbon nanomaterials.

One of the critical issues in the industrial development of fuel cells (e.g., proton exchange membrane fuel cells, direct methanol fuel cells and biofuel cells) is the high cost, serious intermediate tolerance, anode crossover, sluggish kinetics, and poor stability of the platinum (Pt) as the preferred electrocatalysts for the oxygen reduction reaction (ORR) at the cathode. The development of novel noble-metal-free electrocatalysts with low cost, high activity and practical durability for ORR has been considered as one of the most active and competitive fields in chemistry and materials science. In this critical review, we will summarize recent advances on engineering advanced carbon nanomaterials with different dimensions for the rational design and synthesis of noble-metal-free oxygen reduction electrocatalysts including heteroatom-doped carbon nanomaterials, transition metal-based nanoparticle (NP)-carbon nanomaterial composites and especially the stable iron carbide (Fe3C)-based NP-carbon nanomaterial composites. Introducing advanced carbon nanomaterials with high specific surface area and stable structure into the noble-metal-free ORR field has not only led to a maximized electrocatalyst surface area for the electron transfer but also resulted in enhanced electrocatalyst stability for long-term operation. Therefore, the rational design and synthesis of noble-metal-free electrocatalysts based on heteroatoms, transition metal-based NPs and Fe3C-based NP functionalized carbon nanomaterials are of special relevance for their ORR applications, and represents a rapidly growing branch of research. The demonstrated examples in this review will open new directions on designing and optimizing advanced carbon nanomaterials for the development of extremely active and durable earth-abundant cathodic catalysts for fuel cell applications.

In†Situ Raman Monitoring of Silver(I)-Aided Laser-Driven Cleavage Reaction of Cyclobutane.

The cyclobutane cleavage reaction is an important process and has received continuous interest. Herein, we demonstrate the visible laser-driven cleavage reaction of cyclobutane in crystal form by using in situ Raman spectroscopy. Silver(I) coordination-induced strain and thermal effects from the laser irradiation are the two main driving forces for the cleavage of cyclobutane crystals. This work may open up a new avenue for studying cyclobutane cleavage reactions, as compared to the conventional routes using ex situ techniques.

DNA-assisted photoinduced charge transfer between a cationic poly(phenylene vinylene) and a cationic fullerene.

Water-soluble cationic conjugated poly(phenylene vinylene) (PPV) and cationic fullerene were complexed with negatively charged single stranded DNA and double stranded DNA via electrostatic interactions to achieve photoinduced charge transfer with efficiencies as high as those observed from oppositely charged, cationic PPV and anionic fullerene but with distinctly different quenching mechanisms.

Multifunctional polymer-metal nanocomposites via direct chemical reduction by conjugated polymers.

Noble metal nanoparticles (MNPs) have attracted continuous attention due to their promising applications in chemistry, physics, bioscience, medicine and materials science. As an alternative to conventional solution chemistry routes, MNPs can be directly synthesized through a conjugated polymer (CP) mediated technique utilizing the redox chemistry of CPs to chemically reduce the metal ions and modulate the size, morphology, and structure of the MNPs. The as-prepared multifunctional CP-MNP nanocomposites have shown application potentials as highly sensitive surface enhanced Raman spectroscopy (SERS) substrates, effective heterogeneous catalysts for organic synthesis and electrochemistry, and key components for electronic and sensing devices. In this tutorial review, we begin with a brief introduction to the chemical nature and redox properties of CPs that enable the spontaneous reduction of noble metal ions to form MNPs. We then focus on recent progress in control over the size, morphology and structure of MNPs during the conjugated polymer mediated syntheses of CP-MNP nanocomposites. Finally, we highlight the multifunctional CP-MNP nanocomposites toward their applications in sensing, catalysis, and electronic devices.

Recent Progress of Low-Toxicity Poor-Lead All-Inorganic Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (PSCs) have achieved an impressive certified efficiency of 25.7%, which is comparatively higher than that of commercial silicon solar cells (23.3%), showing great potential toward commercialization. However, the low stability and high toxicity due to the presence of volatile organic components and toxic metal lead in the perovskites pose significant challenges. To obtain robust and low-toxicity PSCs, substituting organic cations with pure inorganic cations, and partially or fully replacing the toxic Pb with environmentally benign metals, is one of the promising methods. To date, continuous efforts have been made toward the construction of highly performed low-toxicity inorganic PSCs with astonishing breakthroughs. This review article provides an overview of recent progress in inorganic PSCs in terms of lead-reduced and lead-free compositions. The physical properties of poor-lead all-inorganic perovskites are discussed to unveil the major challenges in this field. Then, it reports notable achievements for the experimental studies to date to figure out feasible methods for efficient and stable poor-lead all-inorganic PSCs. Finally, a discussion of the challenges and prospects for poor-lead all-inorganic PSCs in the future is presented.

B-Site Co-Doping Coupled with Additive Passivation Pushes the Efficiency of Pb-Sn Mixed Inorganic Perovskite Solar Cells to Over 17.

Pb-Sn mixed inorganic perovskite solar cells (PSCs) have garnered increasing interest as a viable solution to mitigate the thermal instability and lead toxicity of hybrid lead-based PSCs. However, the relatively poor structural stability and low device efficiency hinder its further development. Herein, high-performance manganese (Mn)-doped Pb-Sn-Mn-based inorganic perovskite solar cells (PSCs) are successfully developed by introducing Benzhydroxamic Acid (BHA) as multifunctional additive. The incorporation of smaller divalent Mn cations contributes to a contraction of the perovskite crystal, leading to an improvement in structural stability. The BHA additive containing a reductive hydroxamic acid group (O═C-NHOH) not only mitigates the notorious oxidation of Sn2+ but also interacts with metal ions at the B-site and passivates related defects. This results in films with high crystallinity and low defect density. Moreover, the BHA molecules tend to introduce a near-vertical dipole moment that parallels the built-in electric field, thus facilitating charge carrier extraction. Consequently, the resulting device delivers a champion PCE as high as 17.12%, which represents the highest reported efficiency for Pb-Sn-based inorganic PSCs thus far. Furthermore, the BHA molecule provides an in situ encapsulation of the perovskite grain boundary, resulting in significant enhancement of device air stability.

Super-Poissonian statistics of photon emission from single CdSe-CdS core-shell nanocrystals coupled to metal nanostructures.

We demonstrate that photon antibunching observed for individual nanocrystal quantum dots (NQDs) can be transformed into photon bunching characterized by super-Poissonian statistics when they are coupled to metal nanostructures (MNs). This observation indicates that, while the quantum yield of a biexciton (Q(2X)) is lower than that of a single exciton (Q(1X)) in freestanding NQDs, Q(2X) becomes greater than Q(1X) in NQDs coupled to MNs. This unique phenomenon is attributed to metal-induced quenching with a rate that scales more slowly with exciton multiplicity than the radiative decay rate and dominates over other nonradiative decay channels for both single excitons and biexcitons.

Lipid membrane domains for the selective adsorption and surface patterning of conjugated polyelectrolytes.

Conjugated polyelectrolytes (CPEs) are promising materials for generating optoelectronics devices under environmentally friendly processing conditions, but challenges remain to develop methods to define lateral features for improved junction interfaces and direct optoelectronic pathways. We describe here the potential to use a bottom-up approach that employs self-assembly in lipid membranes to form structures to template the selective adsorption of CPEs. Phase separation of gel phase anionic lipids and fluid phase phosphocholine lipids allowed the formation of negatively charged domain assemblies that selectively adsorb a cationic conjugated polyelectrolyte (P2). Spectroscopic studies found the adsorption of P2 to negatively charged membranes resulted in minimal structural change of the solution phase polymer but yielded an enhancement in fluorescence intensity (~50%) due to loss of quenching pathways. Fluorescence microscopy, dynamic light scattering, and AFM imaging were used to characterize the polymer-membrane interaction and the polymer-bound domain structures of the biphasic membranes. In addition to randomly formed circular gel phase domains, we also show that predefined features, such as straight lines, can be directed to form upon etched patterns on the substrate, thus providing potential routes toward the self-organization of optoelectronic architectures.

Electrospinning of Biodegradable, Monolithic Membrane with Distinct Bimodal Micron-Sized Fibers and Nanofibers for High Efficiency PMs Removal.

Atmospheric particulate matter (PMs) pollution has raised increasing public concerns, especially with the outbreak of COVID-19. The preparation of high-performance membranes for air filtration is of great significance. Herein, the biosynthetic polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was adopted to create a hierarchical structure and biodegradable nonwoven membrane for PMs filtration through a facile directly electrospinning method. The as-prepared membranes with hierarchical structure contain abundant nanowires (5-100 nm) and microfibers (2-5 µm) with different diameter (1000-5000 nm). We have achieved realization of formation mechanisms of such bimodal micro- and nanofibers, which stem from the branching of microfiber at early stage of electrospinning. The PHBV membranes exhibit a very high PM0.3 removal efficiency of 99.999% and PM2.5 removal efficiency of 100% with 0.077% standard atmospheric pressure in the air flow speed of 5.3 cm/s. More importantly, the PHBV membranes can be completely disintegrated within 1 week under composted conditions, indicating the great biodegradability of PHBV membranes. Our work provides insights for the development of biodegradable, high performance air filters for pollutants, molds, bacteria, and viruses.

Surface oxidation protection strategy of CoS2 by V2O5 for electrocatalytic hydrogen evolution reaction.

Transition metal sulfides (TMSs) are promising electrocatalysts for hydrogen evolution reaction (HER), while TMSs usually suffer from inevitable surface oxidation in air, and the impact of the surface oxidation on their HER catalytic activity remains unclear. Herein, we demonstrate an effective strategy for reducing the surface oxidation degree of easily oxidized CoS2 by introducing glued vanadium pentoxide (V2O5) nanoclusters, taking advantage of the preferential adsorption and strong interaction between high-valence V and O2. Combining oxidation protection and elaborate oxidation control experiments reveal that reduced surface oxidation degree of CoS2 is conducive to affording promising HER catalytic performance, as the oxidized surface of CoS2 can hinder the dissociation of water and thus is harmful to the HER process. Direct evidence is provided that surface oxidation should be carefully considered for TMS-based HER catalysts. The present work not only develops a new strategy for protecting CoS2 from surface oxidation, but also provides deep insight into the impact of surface oxidation on the HER performance of transition metal compounds.

Synergistic Optimization of Buried Interface by Multifunctional Organic-Inorganic Complexes for Highly Efficient Planar Perovskite Solar Cells.

For the further improvement of the power conversion efficiency (PCE) and stability of perovskite solar cells (PSCs), the buried interface between the perovskite and the electron transport layer is crucial. However, it is challenging to effectively optimize this interface as it is buried beneath the perovskite film. Herein, we have designed and synthesized a series of multifunctional organic-inorganic (OI) complexes as buried interfacial material to promote electron extraction, as well as the crystal growth of the perovskite. The OI complex with BF4- group not only eliminates oxygen vacancies on the SnO2 surface but also balances energy level alignment between SnO2 and perovskite, providing a favorable environment for charge carrier extraction. Moreover, OI complex with amine (- NH2) functional group can regulate the crystallization of the perovskite film via interaction with PbI2, resulting in highly crystallized perovskite film with large grains and low defect density. Consequently, with rational molecular design, the PSCs with optimal OI complex buried interface layer which contains both BF4- and -NH2 functional groups yield a champion device efficiency of 23.69%. More importantly, the resulting unencapsulated device performs excellent ambient stability, maintaining over 90% of its initial efficiency after 2000 h storage, and excellent light stability of 91.5% remaining PCE in the maximum power point tracking measurement (under continuous 100 mW cm-2 light illumination in N2 atmosphere) after 500 h.

Enhancing Moisture and Electrochemical Stability of the Li5.5PS4.5Cl1.5 Electrolyte by Oxygen Doping.

Chlorine-rich argyrodite-type solid electrolyte Li5.5PS4.5Cl1.5 has been a promising choice for solid-state batteries (SSBs) because of its ultrafast Li-ion conduction. However, the poor air/moisture stability and low electrochemical stability with pristine high-voltage cathodes hinder their applications. Herein, O-substituted Li5.5PS4.5-xOxCl1.5 (x = 0, 0.075, 0.175, and 0.25) solid electrolytes are successfully synthesized. Among them, Li5.5PS4.425O0.075Cl1.5 delivers high ionic conductivity, improved moisture resistance, and enhanced electrochemical stability in higher voltage windows. SSBs using Li5.5PS4.425O0.075Cl1.5 show higher capacities and superior cyclability than those using Li5.5PS4.5Cl1.5 combined with a pristine LiNi0.8Mn0.1Co0.1O2 cathode when operated at a high end-of-charge voltage of 4.5 V (vs Li+/Li0). Moreover, the batteries exhibit outstanding performance in a wide temperature range. This work provides a strategy to modify the inherent drawbacks of sulfide electrolytes, promoting their practical applications.