Positively Charged Amino Acid-Modulated Interfacial Chemistry and Deposition Textures for Highly Reversible Zinc Anodes.

Interfacial active water molecule-induced parasitic reactions and stochastic Zn2+ transport-caused dendrite issue significantly impede the implementation of aqueous Zn-ion batteries. Herein, three positively charged amino acids, namely arginine, histidine, and lysine, were utilized as adsorption-type electrolyte additives to enhance the stability and reversibility of Zn anodes. Combined theoretical and experimental analyses verified that these amino acid cations can synergistically modulate the interfacial microenvironment and promote orientational Zn deposition. The adsorbed amino acid cations reconfigured the interfacial electric double layer structure, forming SO42-- and H2O-poor interfaces, thereby retarding hydrogen evolution and corrosion side reactions. Simultaneously, the preferential adsorption of the amino acid cations at specific facets induced crystallographic orientational Zn deposition along unterminated facets. Three deposition architectures, namely planar texture, subvertical alignment, and vertical erection, were obtained, all effectively inhibiting dendrite formation. Consequently, symmetric cells with the three amino acid cations exhibited high stripping/plating reversibility of over 2000 cycles at 5 mA cm-2. Moreover, MnO2-based full cells exhibited markedly improved stabilities compared with their additive-free counterparts.

A Keggin Al13 -Montmorillonite Modified Separator Retards the Polysulfide Shuttling and Accelerates Li-Ion Transfer in Li-S Batteries.

The commercialization of Li-S batteries as a promising energy system is terribly impeded by the issues of the shuttle effect and Li dendrite. Keggin Al13 -pillared montmorillonite (AlMMT), used as the modified film of the separator together with super-P and poly (vinylidene fluoride) (PVDF), has a good chemical affinity to lithium polysulfide (LiPS) to retard the polysulfide shuttling, excellent electrolyte wettability, and a stable structure, which can improve the rate capability and cycling stability of Li-S batteries. Density function theory (DFT) calculations reveal the strong adsorption ability of AlMMT for LiPS. Consequently, the modified film allows Li-S batteries to reach 902 mAh g-1 at 0.2C after 200 cycles and 625 mAh g-1 at 1C after 1000 cycles. More importantly, a high reversible areal capacity of 4.04 mAh cm-2 can be realized under a high sulfur loading of 6.10 mg cm-2 . Combining the merits of rich resources of montmorillonite, prominent performance, simple operation and cost-effectiveness together, this work exploits a new route for viable Li-S batteries for applications.

Waterwheel-inspired rotating evaporator for efficient and stable solar desalination even in saturated brine.

Solar desalination is one of the most promising technologies to address global freshwater shortages. However, traditional evaporators encounter the bottleneck of reduced evaporation rate or even failure due to salt accumulation in high-salinity water. Inspired by ancient waterwheels, we have developed an adaptively rotating evaporator that enables long-term and efficient solar desalination in brines of any concentration. The evaporator is a sulphide-loaded drum-type biochar. Our experiments and numerical simulations show that this evaporator, thanks to its low density and unique hydrophilic property, rotates periodically under the center-of-gravity shift generated by salt accumulation, achieving self-removal of salt. This allows it to maintain a high evaporation rate of 2.80 kg m-2 h-1 within 24 h even in saturated brine (26.47%), which was not achieved previously. This proof-of-concept work therefore demonstrates a concentration- and time-independent, self-rotation-induced solar evaporator.

Rational engineering yolk-shell In2S3@void@carbon hybrid as polysulfide-absorbable sulfur host for high-performance lithium-sulfur batteries.

The slow redox kinetics and shuttling behavior of the intermediate lithium polysulfides constrain the further development of lithium-sulfur (Li-S) electrochemistry. A yolk-shell In2S3@void@carbon hybrid engineered to host the sulfur for Li-S batteries is prepared by using a multi-layered assembly method. The In2S3/electrolyte interface acted as powerful adsorption and activation sites for soluble polysulfides, which is demonstrated using density functional theory (DFT) calculations. Moreover, the carbon shell provides redundancy for volume-changes during the cycles. The results indicate that yolk-shell In2S3@S@C hybrid cathode shows good reversibility and rate capability, which preserves 563.6 mA h g-1 after 500 cycles at 0.5 C, indicating the potential for developing high-performance battery systems.

Effect of MnO2 Morphology on Kinetics and Stability in Zinc-Ion Batteries.

Research on zinc-ion batteries (ZIBs) with manganese-based cathodes has been severely hindered by their poor cycle stability. This study explores the fundamental parameters that affect the cycle stability of battery systems from a structural stability perspective. MnO2 electrodes with different classical morphologies and sizes were synthesized via a temperature-controlled coprecipitation strategy. The effects of the morphology and size of the MnO2 on the overall electrical properties and kinetics of ZIBs were analyzed and compared. The one-dimensional nanofibrous α-MnO2 produced using this method exhibited the most stable nanostructure with a favorable aspect ratio, which resulted in faster chemical kinetics. A more uniform particle distribution and better aspect ratios not only enabled a faster ion migration rate but also affected the remolding of the anode morphology. After 2000 cycles at a high current density of 1 A g-1, the material maintained an excellent discharge-specific capacity, highlighting it as a promising electrode material for ZIBs. The construction of nanoenergy materials with controllable morphologies and sizes will significantly advance battery applications.

Long-Cycling-Life Sodium-Ion Battery Using Binary Metal Sulfide Hybrid Nanocages as Anode.

Due to the relatively high capacity and lower cost, transition metal sulfides (TMS) as anode show promising potential in sodium-ion batteries (SIBs). Herein, a binary metal sulfide hybrid consisting of carbon encapsulated CoS/Cu2 S nanocages (CoS/Cu2 S@C-NC) is constructed. The interlocked hetero-architecture filled with conductive carbon accelerates the Na+ /e- transfer, thus leading to improved electrochemical kinetics. Also the protective carbon layer can provide better volume accommondation upon charging/discharging. As a result, the battery with CoS/Cu2 S@C-NC as anode displays a high capacity of 435.3 mAh g-1 after 1000 cycles at 2.0 A g-1 (≈3.4 C). Under a higher rate of 10.0 A g-1 (≈17 C), a capacity of as high as 347.2 mAh g-1 is still remained after long 2300 cycles. The capacity decay per cycle is only 0.017%. The battery also exhibits a better temperature tolerance at 50 and -5 °C. A low internal impedance analyzed by X-ray diffraction patterns and galvanostatic intermittent titration technique, narrow band gap, and high density of states obtained by first-principle calculations of the binary sulfides, ensure the rapid Na+ /e- transport. The long-cycling-life SIB using binary metal sulfide hybrid nanocages as anode shows promising applications in versatile electronic devices.

Far-infrared transparent conductors.

The long-standing challenge in designing far-infrared transparent conductors (FIRTC) is the combination of high plasma absorption edge (λp) and high conductivity (σ). These competing requirements are commonly met by tuning carrier concentration or/and effective carrier mass in a metal oxide/oxonate with low optical dielectric constant (εopt = 2-7). However, despite the high σ, the transparent band is limited to mid-infrared (λp < 5 µm). In this paper, we break the trade-off between high σ and λp by increasing the "so-called constant" εopt that has been neglected, and successfully develop the material family of FIRTC with εopt > 15 and λp > 15 µm. These FIRTC crystals are mainly octahedrally-coordinated heavy-metal chalcogenides and their solid solutions with shallow-level defects. Their high εopt relies on the formation of electron-deficiency multicenter bonds resulting in the great electron-polarization effect. The new FIRTC enables us to develop the first "continuous film" type far-infrared electromagnetic shielder that is unattainable using traditional materials. Therefore, this study may inaugurate a new era in far-infrared optoelectronics.

Synthesis of unconventional Pd-Se nanoparticles for phase-dependent ethanol electrooxidation.

By tuning the amount of the Se precursors during the synthesis, orthorhombic PdSe2, cubic Pd17Se15, and monoclinic Pd7Se2 nanoparticles are synthesized, which show phase-dependent electrocatalysis for the ethanol oxidation reaction. This work advances the controllable synthesis of transition metal selenides and inspires their applications in electrocatalysis.

A blade-like CoZn metal organic framework-based flexible quasi-solid Zn-ion battery.

Wearable flexible electronics has become more and more significant and popular in daily life. Here, a flexible quasi-solid Zn-ion battery consisting of CoZn-metal organic frameworks (MOFs) grown on carbon cloth as an all-in-one cathode working with a hydrogel electrolyte is developed. CoZn MOFs display a blade-like morphology, which is significant for rapid transfer of ions and electrons. The battery bending at angles from 0° to 180° displays high capacities and good capacity retention, and the capacity remains stable as the flexible battery twists to 90°. In addition, the capacity exceeds 101.4 mA h g-1 as the battery is folded to 180° for 30 times, which indicates that the developed Zn-ion batteries would be applicable for a large variety of wearable devices such as foldable cellphones and pads.

Introducing High-Valence Iridium Single Atoms into Bimetal Phosphides toward High-Efficiency Oxygen Evolution and Overall Water Splitting.

Single atoms are superior electrocatalysts having high atomic utilization and amazing activity for water oxidation and splitting. Herein, this work reports a thermal reduction method to introduce high-valence iridium (Ir) single atoms into bimetal phosphide (FeNiP) nanoparticles toward high-efficiency oxygen evolution reaction (OER) and overall water splitting. The presence of high-valence single Ir atoms (Ir4+ ) and their synergistic interaction with Ni3+ species as well as the disproportionation of Ni3+ assisted by Fe collectively contribute to the exceptional OER performance. In specific, at appropriate Ir/Ni and Fe/Ni ratios, the as-prepared Ir-doped FeNiP (Ir25 -Fe16 Ni100 P64 ) nanoparticles at a mass loading of only 35 µg cm-2 show the overpotential as low as 232 mV at 10 mA cm-2 and activity as high as 1.86 A mg-1 at 1.5 V versus RHE for OER in 1.0 m KOH. Computational simulations confirm the vital role of high-valence Ir to weaken the adsorption of OER intermediates, favorable for accelerating OER kinetics. Impressively, a Pt/C||Ir25 -Fe16 Ni100 P64 two-electrode alkaline electrolyzer affords a current density of 10 mA cm-2 at a low cell voltage of 1.42 V, along with satisfied stability. An AA battery with a nominal voltage of 1.5 V can drive overall water splitting with obvious bubbles released.

A Foldable Aqueous Zn-Ion Battery with Gear-Structured Composite as Freestanding Cathode.

A foldable battery with high flexibility provides great potential in various wearable electronic devices for health and fitness tracking, chronic disease management, performance monitoring, navigation tracking, and portable gears for soldiers. We report a highly flexible, self-healing Zn-ion battery with a free-standing cathode that is composed of a 3D gear-like NH4 V4 O10 @C composite on carbon paper. The battery retained a capacity of up to 102.4 mAh g-1 even after being folded 60 times with a high angle of 180°. An aqueous hydrogel consisting polyvinyl alcohol, glycerin and Zn(CF3 SO3 )2 was used as electrolyte, which showed as high as 580 % tensile strain under a loading weight of 78 N. The battery exhibited a better capacity retention of over 100 mAh g-1 and Coulombic efficiency of over 99.8 % after cutting and twisting to 90°, thereby indicating a great self-healing performance. The gear-like geometry greatly improved the volume accommodation due to the increased interval space between the blades and the outward configuration. Meanwhile the Zn2+ ionic conductivity was improved by rapid re-binding of many existing hydroxy groups from the electrolyte and the enhanced contact surface area and diffusion route from the cathode material. The highly flexible, safe aqueous Zn-ion battery opens a practical way to power various carry-on electronics under mechanical agitation.

Metal-coordination and surface adhesion-assisted molding enabled strong, water-resistant carboxymethyl cellulose films.

Developing renewable and biodegradable materials derived from cellulose is an attractive strategy to replace petroleum-derived plastics. In this study, metal ions (Cu2+, Fe3+, and Al3+) were added as a green binder into carboxymethyl cellulose (CMC) films to improve their mechanical properties and water resistance capacity. The tensile strengths of CMCAl3+ films were 133 MPa and 99 MPa at 43 % and 97 % humidity, respectively, which were comparable to or greater than those of the majority of commercially available plastics. Additionally, we proposed an interfacial adhesion-assisted molding strategy for forming cellulose-based films, avoiding film wrinkles and unevenness during drying and metal-coordination formation. The resultant films exhibited high transparency, excellent mechanical properties, water resistance capacity, ultraviolet light (UV) shielding, and antibacterial activity. In summary, the biodegradable, eco-friendly, excellent application performance, and adaptability of CMCMn+ (Mn+: polyvalent metal ions) films open new prospects as a viable alternative to non-biodegradable plastics.

Active Oxygen Functional Group Modification and the Combined Interface Engineering Strategy for Efficient Hydrogen Peroxide Electrosynthesis.

Cathodic catalytic activity and interfacial mass transfer are key factors for efficiently generating hydrogen peroxide (H2O2) via a two-electron oxygen reduction reaction (ORR). In this work, a carbonized carboxymethyl cellulose (CMC)-reduced graphene oxide (rGO) synthetic fabric cathode was designed and constructed to improve two-electron ORR activity and interfacial mass transfer. Carbonized CMC exhibits abundant active carboxyl groups and excellent two-electron ORR activity with an H2O2 selectivity of approximately 87%, higher than that of rGO and other commonly used carbonaceous catalysts. Carbonizing CMC and the agglomerates formed from it restrain the restacking of rGO sheets and thus create abundant meso/macroporous channels for the interfacial mass transfer of oxygen and H2O2. Thus, the as-constructed carbonized CMC-rGO synthetic fabric cathode exhibits exceptional H2O2 electrosynthesis performance with 11.94 mg·h-1·cm-2 yield and 82.32% current efficiency. The sufficient active sites and mass-transfer channels of the cathode also ensure its practical application performance at high current densities, which is further illustrated by the rapid organic pollutant degradation via the H2O2-based electro-Fenton process.

A Magnesium/Lithium Hybrid-Ion Battery with Modified All-Phenyl-Complex-Based Electrolyte Displaying Ultralong Cycle Life and Ultrahigh Energy Density.

Magnesium/lithium hybrid-ion batteries (MLHBs) combine the advantages of high safety and fast ionic kinetics, which enable them to be promising emerging energy-storage systems. Here, a high-performance MLHB using a modified all-phenyl complex with a lithium bis(trifluoromethanesulfonyl)imide electrolyte and a NiCo2S4 cathode on a copper current collector is developed. A reversible conversion involving a copper collector with NiCo2S4 efficiently avoids the electrolyte dissociation and diffusion difficulties of Mg2+ ions, enabling low polarization and fast redox, which is verified by X-ray absorption near edge structure analysis. Such combination affords the best MLHB among all those ever reported, with a reversible capacity of 204.7 mAh g-1 after 2600 cycles at 2.0 A g-1, and delivers an ultrahigh full electrode-basis energy density of 708 Wh kg-1. The developed MLHB also achieves good rate performance and temperature tolerance at -10 and 50 °C with a low electrolyte consumption. The hybrid-ion battery system presented here could inspire a broad set of engineering potentials for high-safety battery technologies and beyond.

Catalytic oxidation of polystyrene to aromatic oxygenates over a graphitic carbon nitride catalyst.

The continuous increase in manufacturing coupled with the difficulty of recycling of plastic products has generated huge amounts of waste plastics. Most of the existing chemical recycling and upcycling methods suffer from harsh conditions and poor product selectivity. Here we demonstrate a photocatalytic method to oxidize polystyrene to aromatic oxygenates under visible light irradiation using heterogeneous graphitic carbon nitride catalysts. Benzoic acid, acetophenone, and benzaldehyde are the dominant products in the liquid phase when the conversion of polystyrene reaches >90% at 150 °C. For the transformation of 0.5 g polystyrene plastic waste, 0.36 g of the aromatic oxygenates is obtained. The reaction mechanism is also investigated with various characterization methods and procedes via polystyrene activation to form hydroxyl and carbonyl groups over its backbone via C-H bond oxidation which is followed by oxidative bond breakage via C-C activation and further oxidation processes to aromatic oxygenates.

3D Hydrogel Evaporator with Vertical Radiant Vessels Breaking the Trade-Off between Thermal Localization and Salt Resistance for Solar Desalination of High-Salinity.

Delivering sufficient water to the evaporation surface/interface is one of the most widely adopted strategies to overcome salt accumulation in solar-driven interfacial desalination. However, water transport and heat conduction loss are positively correlated, resulting in the trade-off between thermal localization and salt resistance. Herein, a 3D hydrogel evaporator with vertical radiant vessels is prepared to surmount the long-standing trade-off, thereby achieving high-rate and stable solar desalination of high-salinity. Experiments and numerical simulations reveal that the unique hierarchical structure, which consists of a large vertical vessel channel, radiant vessels, and porous vessel walls, facilitates strong self-salt-discharge and low longitudinal thermal conductivity. With the structure employed, a groundbreaking comprehensive performance, under one sun illumination, of evaporation rate as high as 3.53 kg m-2  h-1 , salinity of 20 wt%, and a continuous 8 h evaporation is achieved, which thought to be the best reported result from a salt-free system. This work showcases the preparation method of a novel hierarchical microstructure, and also provides pivotal insights into the design of next-generation solar evaporators of high-efficiency and salt tolerance.

Catalytic Transformation of PET and CO2 into High-Value Chemicals.

Polyethylene terephthalate (PET) and CO2 , two chemical wastes that urgently need to be transformed in the environment, are converted simultaneously in a one-pot catalytic process through the synergistic coupling of three reactions: CO2 hydrogenation, PET methanolysis and dimethyl terephthalate (DMT) hydrogenation. More interestingly, the chemical equilibria of both reactions were shifted forward due to a revealed dual-promotion effect, leading to significantly enhanced PET depolymerization. The overall methanol yield from CO2 hydrogenation exceeded the original thermodynamic equilibrium limit since the methanol was in situ consumed in the PET methanolysis. The degradation of PET by a stoichiometric ratio of methanol was significantly enhanced because the primary product, DMT was hydrogenated to dimethyl cyclohexanedicarboxylate (DMCD) or p-xylene (PX). This synergistic catalytic process provides an effective way to simultaneously recycle two wastes, polyesters and CO2 , for producing high-value chemicals.

Lignocellulosic nanofibril aerogel via gas phase coagulation and diisocyanate modification for solvent absorption.

Cellulose-based aerogels are considered to be carriers that can absorb oils and organic solvents owing to the merits of low density and high surface area. However, the natural hydrophility and poor mechanical strength often obstruct their widespread applications. In this work, Miscanthus-based dual cross-linked lignocellulosic nanofibril (LCNF) aerogels were prepared by gas phase coagulation and methylene diphenyl dissocyanate (MDI) modification. Due to physical and chemical cross-linking strategies, the optimally 4 M-LCNF aerogels had high surface area of 157.9 m2/g, water contact angle of 138.1°, and enhanced compression properties. Moreover, the modified aerogels exhibited absorption performance for various organic solvents, and the maximal absorption capacity of chloroform was 42 g/g aerogel. Because LCNF was directly produced from Miscanthus without using bleaching reagents, this research provided a more sustainable methodology to utilize lignocelluloses to design robust aerogels to deal with the leakage of oil and organic solvents in industrial applications.

Increased crystallinity of RuSe2/carbon nanotubes for enhanced electrochemical hydrogen generation performance.

Ru-Based catalysts are significant in the green hydrogen generation via the electrochemical water-splitting reaction. Herein, it is found that the increased crystallinity of cubic RuSe2 nanoparticles anchored over carbon nanotubes (RuSe2/CNTs) could largely increase the hydrogen generation performance both in acidic and alkaline electrolytes. The freshly prepared RuSe2/CNTs with low crystallinity had a very low catalytic performance for the HER, while the catalytic ability could be largely boosted by facile thermal annealing at 650 °C in an N2 atmosphere, resulting from the increased crystallinity and electronic effect. The crystal structure enhancement of the RuSe2 nanoparticles was well supported by the X-ray diffraction technique and the lattice fringes in the high-resolution transmission electron microscopy images. As a result, the catalyst exhibited largely improved catalytic performance compared to the freshly prepared RuSe2/CNTs; specifically, the overpotentials of 48 and 64 mV were required to drive 10 mA cm-2 in alkaline and acidic media when loaded on a glassy carbon electrode, much less than those of 109 and 120 mV for the freshly prepared RuSe2/CNTs; the catalytic performance in the alkaline electrolyte was even close to that of the commercial Pt/C catalyst. Correspondingly, the improved catalytic stability, catalytic kinetics, charge transfer ability and catalytic efficiency of the active sites were also observed. The current work shows an effective approach and important understanding for catalytic performance enhancement via increased crystallinity by facile thermal annealing.

Gas-solid fluidization modification of calcium carbonate for high-performance poly (butylene adipate-co-terephthalate) (PBAT) composites.

Modifying biodegradable poly (butylene adipate-co-terephthalate) (PBAT) plastic with inorganic fillers is critical for improving its overall performance, lowering the costs, and expanding its application scope. The chemical modification method for the inorganic filler determines the application performance of PBAT composites. In this work, gas-solid fluidization method was developed as a simple, efficient, and scalable strategy for chemically modifying CaCO3 filler. The modified CaCO3 filler was mixed with PBAT and melt extruded to prepare biodegradable PBAT/CaCO3 composites. The characterization results show that gas-solid fluidization method combines the traditional wet modification method's excellent modification effect with the scalability of the traditional dry modification method. The effects of modification methods and amount of CaCO3 filling on the crystallinity, mechanical, and rheological properties of PBAT/CaCO3 composites were compared. The results demonstrated that PBAT/CaCO3 composites containing 30% gas-solid fluidization modified CaCO3 could still maintain excellent overall performance. As a result, this work provides a simple, efficient, and scalable method for chemically modifying inorganic fillers and preparing biodegradable composites.