A Rechargeable "Rocking Chair" Type Zn-CO2 Battery.

Rising global temperatures and critical energy shortages have spurred researches into CO2 fixation and conversion within the realm of energy storage such as Zn-CO2 batteries. However, traditional Zn-CO2 batteries employ double-compartment electrolytic cells with separate carriers for catholytes and anolytes, diverging from the "rocking chair" battery mechanism. The specific energy of these conventional batteries is constrained by the solubility of discharge reactants/products in the electrolyte. Additionally, H2O molecules tend to trigger parasitic reactions at the electrolyte/electrode interfaces, undermining the long-term stability of Zn anodes. In this report, we introduce an innovative "rocking chair" type Zn-CO2 battery that utilizes a weak-acidic zinc trifluoromethanesulfonate aqueous electrolyte compatible with both cathode and anode. This design minimizes side reactions on the Zn surface and leverages the high catalytic activity of the cathode material, allowing the battery to achieve a substantial discharge capacity of 6734 mAh g-1 and maintain performance over 65 cycles. Moreover, the successful production of pouch cells demonstrates the practical applicability of Zn-CO2 batteries. Electrode characterizations confirm superior electrochemical reversibility, facilitated by solid discharge products of ZnCO3 and C. This work advances a "rocking chair" Zn-CO2 battery with an enhanced specific energy and a reversible pathway, providing a foundation for developing high-performance metal-CO2 batteries.

Dual-Signal Triple-Mode Optical Sensing Platform for Assisting in the Diagnosis of Kidney Disorders.

As known biomarkers of kidney diseases, N-acetyl-ß-d-glucosaminidase (NAG) and ß-galactosidase (ß-GAL) are of great importance for the diagnosis and treatment of diseases. The feasibility of using multiplex sensing methods to simultaneously report the outcome of the two enzymes in the same sample is even more alluring. Herein, we establish a simple sensing platform for the concurrent detection of NAG and ß-GAL using silicon nanoparticles (SiNPs) as a fluorescent indicator synthesized by a one-pot hydrothermal route. p-Nitrophenol (PNP), as a common enzymatic hydrolysis product of the two enzymes, led to the attenuation of fluorometric signal caused by the inner filter effect on SiNPs, the enhancement of colorimetric signal due to the increase of intensity of the characteristic absorption peak at around 400 nm with increasing reaction time, and the changes of RGB values of images obtained through a color recognition application on a smartphone. The fluorometric/colorimetric approach combined with the smartphone-assisted RGB mode was able to detect NAG and ß-GAL with good linear response. Applying this optical sensing platform to clinical urine samples, we found that the two indicators in healthy individuals and patients (glomerulonephritis) with kidney diseases were significantly different. By expanding to other renal lesion-related specimens, this tool may show great potentials in clinical diagnosis and visual inspection.

Ultrabright silicon nanoparticle fluorescence probe for sensitive detection of cholesterol in human serum.

A highly sensitive fluorescence-based assay for cholesterol detection was developed using water-dispersible green-emitting silicon nanoparticles (SiNPs) as a fluorescence indicator and enzyme-catalyzed oxidation product PPDox (Bandrowski's base) as a quencher. The SiNPs were facilely synthesized via a simple, one-step hydrothermal treatment using 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (AEEA) as the silicon source, which has ultrahigh quantum yield and low phototoxicity. Under the catalysis of cholesterol oxidase (ChOx), hydrogen peroxide (H2O2) was generated as a result of cholesterol oxidation. Utilizing p-phenylenediamine (PPD) as the substrate for horseradish peroxidase (HRP) in the presence of H2O2 led to the production of PPDox. Based upon the inner filter effect (IFE), the established ultrasensitive fluorescent assay could accurately measure cholesterol. The limit of detection (LOD) of the assay was 0.018 µM with a linear range of 0.025-10 µM. The results for the detection of real serum samples by the proposed assay were comparable to those by a commercial reagent kit, demonstrating that our proposed strategy has high application potential in disease diagnosis and other related biological studies.

Flame-Retardant ADP/PEO Solid Polymer Electrolyte for Dendrite-Free and Long-Life Lithium Battery by Generating Al, P-rich SEI Layer.

The poly(ethylene oxide) solid polymer electrolyte (PEO SPE) has recently received much attention, however, the organic components in the SPE are still flammable. In this paper, we find that the high efficiency halogen-free aluminum (Al) diethyl hypophosphite flame retardant (ADP) is effective in reducing the flammability of PEO SPE. The SEI layer containing Al and phosphorus (P) inhibits the growth of lithium dendrite and enhances the cycle life of the battery. The capacity of a LiFePO4/SPE/Li battery containing ADP is still 123.2 mAh g-1 at 1.0 C and the Coulombic efficiency is as high as 99.95% after 1000 cycles (60 °C). At the same time, Al, P-rich SEI can inhibit the growth of lithium dendrite and the cycle stability of the battery is further enhanced.

A Bridge-Linked Phosphorus-Containing Flame Retardant for Endowing Vinyl Ester Resin with Low Fire Hazard.

The high flammability of vinyl ester resin (VE) significantly limits its widespread application in the fields of electronics and aerospace. A new phosphorus-based flame retardant 6,6'-(1-phenylethane-1,2 diyl) bis (dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (PBDOO), was synthesized using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and acetophenone. The synthesized PBDOO was further incorporated with VE to form the VE/PBDOO composites, which displayed an improved flame retardancy with higher thermal stability. The structure of PBDOO was investigated using Fourier transformed infrared spectrometry (FTIR) and nuclear magnetic resonances (NMR). The thermal stability and flame retardancy of VE/PBDOO composites were investigated by thermogravimetric analysis (TGA), vertical burn test (UL-94), limiting oxygen index (LOI), and cone calorimetry. The impacts of PBDOO weight percentage (wt%) on the flame-retardant properties of the formed VE/PBDOO composites were also examined. When applying 15 wt% PBDOO, the formed VE composites can meet the UL-94 V-0 rating with a high LOI value of 31.5%. The peak heat release rate (PHRR) and the total heat release (THR) of VE loaded 15 wt% of PBDOO decreased by 76.71% and 40.63%, respectively, compared with that of untreated VE. In addition, the flame-retardant mechanism of PBDOO was proposed by analyzing pyrolysis behavior and residual carbon of VE/PBDOO composites. This work is expected to provide an efficient method to enhance the fire safety of VE.

Light-Induced Nonoxidative Coupling of Methane Using Stable Solid Solutions.

Achieving efficient and direct conversion of methane under mild conditions is of great significance for innovations in the chemical industry. However, the efficiency and lifetime of most catalysts remain too far from practical requirements, since it is difficult to break the first C-H bond of methane as well as to suppress the following complete dehydrogenation (or overoxidation) and the resulting carbonaceous deposition (or CO2 ). Here, we report that wurtzite GaN:ZnO solid solutions exhibit unique and unprecedented photocatalytic performances for the nonoxidative coupling of methane at room temperature, exclusively generating ethane with nearly stoichiometric H2 . High conversion rate (>330 µmol g-1 h-1 ), long-term stability (>70 h), and superior coke-resistance were achieved. At 293 K, the methane conversion exceeds 7 %, comparable to the equilibrium conversion of thermal catalysis at 910 K. Mechanistic studies revealed that the N-ZnGa -ON units and the absence of acid sites on the surface played crucial roles in reactivity and coke resistance, respectively.

Constructing a Super-Saturated Electrolyte Front Surface for Stable Rechargeable Aqueous Zinc Batteries.

Rechargeable aqueous zinc batteries (RAZB) have been re-evaluated because of the superiority in addressing safety and cost concerns. Nonetheless, the limited lifespan arising from dendritic electrodeposition of metallic Zn hinders their further development. Herein, a metal-organic framework (MOF) was constructed as front surface layer to maintain a super-saturated electrolyte layer on the Zn anode. Raman spectroscopy indicated that the highly coordinated ion complexes migrating through the MOF channels were different from the solvation structure in bulk electrolyte. Benefiting from the unique super-saturated front surface, symmetric Zn cells survived up to 3000 hours at 0.5 mA cm-2 , near 55-times that of bare Zn anodes. Moreover, aqueous MnO2 -Zn batteries delivered a reversible capacity of 180.3 mAh g-1 and maintained a high capacity retention of 88.9 % after 600 cycles with MnO2 mass loading up to 4.2 mg cm-2 .

A multi-layered Fe2O3/graphene composite with mesopores as a catalyst for rechargeable aprotic lithium-oxygen batteries.

Aprotic Li-O2 batteries have attracted a huge amount of interest in the past decade owing to their extremely high energy density. However, identifying a desirable cathodic catalyst for this promising battery system is one of the biggest challenges at present. In this work, a multi-layered Fe2O3/graphene nanosheets (Fe2O3/GNS) composite with sandwich structure was synthesized using an easy thermal casting method, and served as a cathodic catalyst for aprotic Li-O2 batteries. The aprotic Li-O2 cell with the Fe2O3/GNS catalyst demonstrated a better reversibility, lower overpotential for oxygen evolution, and a higher Coulombic efficiency (close to 100%) than those of pure GNS. An excellent rate performance and good cycle stability were also confirmed. The results, characterized by ex and in situ methods, revealed that the dominant discharge product Li2O2 was decomposed below 4.35 V. This superior electrochemical performance is mainly attributed to the unique sandwich structure of the Fe2O3/GNS catalyst with mesopores, which can provide substantially more catalytic sites and prevent direct contact between carbon and Li2O2.

Recent Advances in Ammonia Synthesis: From Haber-Bosch Process to External Field Driven Strategies.

Ammonia, a pivotal chemical feedstock and a potential hydrogen energy carrier, demands efficient synthesis as a key step in its utilization. The traditional Haber-Bosch process, known for its high energy consumption, has spurred researchers to seek ammonia synthesis under milder conditions. Advances in surface science and characterization technologies have deepened our understanding of the microscopic reaction mechanisms of ammonia synthesis. This article concentrates on gas-solid phase ammonia synthesis, initially exploring the latest breakthroughs and improvements in thermal catalytic synthesis. Building on this, it especially focuses on emerging external field-driven alternatives, such as photocatalysis, photothermal catalysis, and low-temperature plasma catalysis strategies. The paper concludes by discussing the future prospects and objectives of nitrogen fixation technologies. This comprehensive review is intended to provide profound insights for overcoming the inherent thermodynamic and kinetic constraints in traditional ammonia synthesis, thereby fostering a shift towards "green ammonia" production and significantly reducing the energy footprint.

Thermal and Combustion Properties of Biomass-Based Flame-Retardant Polyurethane Foams Containing P and N.

Biomass has been widely used due to its environmental friendliness, sustainability, and low toxicity. In this study, aminophosphorylated cellulose (PNC), a biomass flame retardant containing phosphorus and nitrogen, was synthesized by esterification from cellulose and introduced into polyurethane to prepare flame-retardant rigid polyurethane foam. The combustion properties of the PU and PU/PNC composites were studied using the limiting oxygen index (LOI), UL-94, and cone calorimeter (CCT) methods. The thermal degradation behavior of the PU and PU/PNC composites was analyzed by thermogravimetric analysis (TGA) and thermogravimetric infrared spectroscopy (TG-IR). The char layer after combustion was characterized using SEM, Raman, and XPS. The experimental results showed that the introduction of PNC significantly improved the flame-retardant effect and safety of PU/PNC composites. Adding 15 wt% PNC to PU resulted in a vertical burning grade of V-0 and a limiting oxygen index of 23.5%. Compared to the pure sample, the residual char content of PU/PNC15 in a nitrogen atmosphere increased by 181%, and the total heat release (THR) decreased by 56.3%. A Raman analysis of the char layer after CCT combustion revealed that the ID/IG ratio of PU/PNC15 decreased from 4.11 to 3.61, indicating that the flame retardant could increase the stability of the char layer. The TG-IR results showed that PNC diluted the concentration of O2 and combustible gases by releasing inert gases such as CO2. These findings suggest that the developed PU/PNC composites have significant potential for real-world applications, particularly in industries requiring enhanced fire safety, such as construction, transportation, and electronics. The use of PNC provides an eco-friendly alternative to traditional flame retardants. This research paves the way for the development of safer, more sustainable, and environmentally friendly fire-resistant materials for a wide range of applications.

Boosting a practical Li-CO2 battery through dimerization reaction based on solid redox mediator.

Li-CO2 batteries offer a promising avenue for converting greenhouse gases into electricity. However, the inherent challenge of direct electrocatalytic reduction of inert CO2 often results in the formation of Li2CO3, causing a dip in output voltage and energy efficiency. Our innovative approach involves solid redox mediators, affixed to the cathode via a Cu(II) coordination compound of benzene-1,3,5-tricarboxylic acid. This technique effectively circumvents the shuttle effect and sluggish kinetics associated with soluble redox mediators. Results show that the electrochemically reduced Cu(I) solid redox mediator efficiently captures CO2, facilitating Li2C2O4 formation through a dimerization reaction involving a dimeric oxalate intermediate. The Li-CO2 battery employing the Cu(II) solid redox mediator boasts a higher discharge voltage of 2.8 V, a lower charge potential of 3.7 V, and superior cycling performance over 400 cycles. Simultaneously, the successful development of a Li-CO2 pouch battery propels metal-CO2 batteries closer to practical application.

Highly Efficient Phosphazene-Derivative-Based Flame Retardant with Comprehensive and Enhanced Fire Safety and Mechanical Performance for Polycarbonate.

Polycarbonate (PC) as a widely used engineering plastic that shows disadvantages of flammability and large smoke production during combustion. Although many flame-retardant PCs have been developed, most of them show enhanced flame retardancy but poor smoke suppression or worsened mechanical performance. In this work, a novel nitrogen-phosphorus-sulfur synergistic flame retardant (Pc-FR) was synthesized and incorporated into PC with polytetrafluoroethylene (PTFE). The extremely low content of PC-FR (0.1-0.5 wt%) contributes significantly to the flame retardancy, smoke suppression and mechanical performance of PC. PC/0.3 wt% Pc-FR/0.3 wt% PTFE (PC-P0.3) shows the UL-94 V-0 and LOI of 33.5%. The PHRR, THR, PSPR, PCO and TCO of PC-P0.3 decreased by 39.44%, 14.38%, 17.45%, 54.75% and 30.61%, respectively. The impact strength and storage modulus of PC-P0.1 increased by 7.7 kJ/m2 and 26 MPa, respectively. The pyrolysis mechanism of PC-P0.3 is also revealed. The pyrolysis mechanism of PC-P0.3 is stochastic nucleation and subsequent growth and satisfies the Aevrami-Erofeev equation. The reaction order of PC-P0.3 is 1/2. The activation energy of PC-P0.3 is larger than PC-0, which proves that the Pc-FR can suppress the pyrolysis of the PC. This work offers a direction on how to design high-performance PC.

Integrating Lithium Sulfide as a Single Ionic Conductor Interphase for Stable All-Solid-State Lithium-Sulfur Batteries.

As a very prospective solid-state electrolyte, Li10GeP2S12 (LGPS) exhibits high ionic conductivity comparable to liquid electrolytes. However, severe self-decomposition and Li dendrite propagation of LGPS will be triggered due to the thermodynamic incompatibility with Li metal anode. Herein, by adopting a facile chemical vapor deposition method, an artificial solid electrolyte interphase composed of Li2S is proposed as a single ionic conductor to promote the interface stability of LGPS toward Li. The good electronic insulation coupled with ionic conduction property of Li2S effectively blocks electron transfer from Li to LGPS while enabling smooth passage of Li ions. Meanwhile, the generated Li2S layer remains good interface compatibility with LGPS, which is verified by the stable Li-plating/stripping operation for over 500 h at 0.15 mA cm-2. Consequently, the all-solid-state Li-S batteries (ASSLSBs) with a Li2S layer demonstrate superb capacity retention of 90.8% at 0.2 mA cm-2 after 100 cycles. Even at the harsh condition of 90 °C, the cell can deliver a high reversible capacity of 1318.8 mAh g-1 with decent capacity retention of 88.6% after 100 cycles. This approach offers a new insight for interface modification between LGPS and Li and the realization of ASSLSBs with stable cycle life.

Machine-Learning Enhanced Enantioselective Single-Shot-Single-Molecule ac Stark Spectroscopy.

Enantiodiscrimination with single-molecule and single-shot resolution is fundamental for the understanding of the fate and behavior of two enantiomers in chemical reactions, biological activity, and the function of drugs. However, molecular decoherence gives rise to spectral broadening and random errors, offering major problems for most chiroptical methods in arriving at single-shot-single-molecule resolution. Here, we introduce a machine-learning strategy to solve these problems. Specifically, we focus on the task of single-shot measurement of single-molecule chirality based on enantioselective ac Stark spectroscopy. We find that, in the large-decoherence region, where the ac Stark spectroscopy without machine learning fails to distinguish molecular chirality, in contrast, the machine-learning-assisted strategy still holds a high correct rate of up to about 90%. Beyond this overwhelming superiority, the machine-learning strategy also has considerable robustness against variation of the decoherence rates between the training and testing sets.

Li-intercalated CeO2 as an ideal substrate for boosting ammonia synthesis.

We present a Li-intercalated-CeO2 catalyst that exhibits outstanding activity for ammonia synthesis. The incorporation of Li significantly reduces the activation energy and suppresses hydrogen poisoning of the Ru co-catalysts. As a result, the lithium intercalation enables the catalyst to achieve ammonia production from N2 and H2 at substantially lower operating temperatures.

A fluorescence probe based on carbon dots for determination of dopamine utilizing its self-polymerization.

A rapid and sensitive strategy for sensing dopamine (DA) was proposed based on the fluorescence quenching effects of polydopamine (PDA) on carbon dots (CDs). The green-emission fluorescence CDs were synthesized via a facile one-pot hydrothermal approach by employing p-phenylenediamine and ethanol as reagents. In alkaline environments, DA would polymerize to form PDA on surface of CDs, resulting in the fluorescence quenching of the detection system owing to the effects of fluorescence resonance energy transfer (FERT) and inner filter effect (IFE). The proposed fluorescence probe exhibits good selectivity and sensitivity to DA in the concentration range of 0.1-15 µM, with a limit of detection (LOD) of 37 nM. Results of detecting DA in serum samples indicate the broad potential of the proposed strategy for future application in diagnosis of DA-related diseases.

Biomass-derived polyphosphazene toward simultaneously enhancing the flame retardancy and mechanical properties of epoxy resins.

As one of the most widely used polymers, the intrinsic brittleness and high flammability bring about a stringent requirement for the practical application of epoxy resins (EPs). It is difficult to toughen EP without compromising its mechanical and thermal properties for many conventional toughening agents. Here, a novel furan-derived bio-based polyphosphazene (PFMP) with a flexible backbone and rigid side groups was prepared by the nucleophilic substitution reaction between polydichlorophosphazene (PDCP) and furfuralcohol. The resultant PFMP was incorporated into EP to realize exceptional toughening, strengthening, and flame retardant function. By adding 15% of PFMP, the limit oxygen index value is from 25% (EP) to 33% (EP/PFMP-15) and reaches the UL-94 V-0 rating. According to the cone calorimeter results, EP/PFMP-15 exhibits exceedingly reduced peak heat release rate (pHRR) (50.2%) and total heat release (THR) (49.6%). The significantly increased fire performance index (FPI) and decreased fire growth rate index (FIGRA) of EP/PFMP-15 demonstrate an improvement in its flame retardancy. The catalytic carbonization effect (condensed phase) and radical quenching effect (gas phase) of PFMP account for the greatly improved flame retardancy. Moreover, the impact and tensile tests indicate that PFMP can ameliorate the mechanical performance of EP with a maximum increase of impact strength (111.8%) and elongation at break (35.2%) for EP/PFMP-5. With 15% PFMP added, the tensile strength of EP/PFMP-15 increases by 40.4%. This work demonstrates that PFMP is expected to overcome shortcomings (flammability, toughness, and strength) of EP and spread its applied fields.

Trifunctional imidazolium bromide: a high-efficiency redox mediator for high-performance Li-O2 batteries.

In this work, 1-aminopropyl-3-methylimidazolium bromide (APMImBr) is introduced in dimethyl sulfoxide-based Li-O2 batteries. The Br- functions as a redox mediator to catalyze the decomposition of the Li2O2 products. Meanwhile, the APMIm+ serves as a scavenging agent for superoxide radicals as well as protects the lithium metal anodes via an in situ formed Li3N-rich solid electrolyte interface layer. As a result, the Li-O2 batteries containing APMImBr delivered an enlarged discharge capacity, a reduced charge overpotential of around 0.61 V and a prolonged cyclic life of over 200 cycles.

Bifunctional electrolyte additive MgI2 for improving cycle life in high-efficiency redox-mediated Li-O2 batteries.

Here, MgI2 is introduced as a bifunctional self-defense redox mediator into dimethyl sulfoxide-based Li-O2 batteries. During charging, I- is first oxidized to I3-, which facilitates the decomposition of Li2O2, and thus reduces overpotential. In addition, Mg2+ spontaneously reacts with the Li anode to form a very stable SEI layer containing MgO, which can resist the synchronous attack by the soluble I3- and improve the interface stability between the Li anode and the electrolyte. Therefore, a Li-O2 battery containing MgI2 exhibits an extended cycling life span (400 cycles) and a quite low overpotential (0.6 V).

Binuclear Cu complex catalysis enabling Li-CO2 battery with a high discharge voltage above 3.0 V.

Li-CO2 batteries possess exceptional advantages in using greenhouse gases to provide electrical energy. However, these batteries following Li2CO3-product route usually deliver low output voltage (<2.5 V) and energy efficiency. Besides, Li2CO3-related parasitic reactions can further degrade battery performance. Herein, we introduce a soluble binuclear copper(I) complex as the liquid catalyst to achieve Li2C2O4 products in Li-CO2 batteries. The Li-CO2 battery using the copper(I) complex exhibits a high electromotive voltage up to 3.38 V, an increased output voltage of 3.04 V, and an enlarged discharge capacity of 5846 mAh g-1. And it shows robust cyclability over 400 cycles with additional help of Ru catalyst. We reveal that the copper(I) complex can easily capture CO2 to form a bridged Cu(II)-oxalate adduct. Subsequently reduction of the adduct occurs during discharge. This work innovatively increases the output voltage of Li-CO2 batteries to higher than 3.0 V, paving a promising avenue for the design and regulation of CO2 conversion reactions.