Promoting Oxygen Evolution Electrocatalysis by Coordination Engineering in Cobalt Phosphate.

Understanding the structure-activity correlation is an important prerequisite for the rational design of high-efficiency electrocatalysts at the atomic level. However, the effect of coordination environment on electrocatalytic oxygen evolution reaction (OER) remains enigmatic. In this work, the regulation of proton transfer involved in water oxidation by coordination engineering based on Co3(PO4)2 and CoHPO4 is reported. The HPO4 2- anion has intermediate pKa value between Co(II)-H2O and Co(III)-H2O to be served as an appealing proton-coupled electron transfer (PCET) induction group. From theoretical calculations, the pH-dependent OER properties, deuterium kinetic isotope effects, operando electrochemical impedance spectroscopy (EIS) and Raman studies, the CoHPO4 catalyst beneficially reduces the energy barrier of proton hopping and modulates the formation energy of high-valent Co species, thereby enhancing OER activity. This work demonstrates a promising strategy that involves tuning the local coordination environment to optimize PCET steps and electrocatalytic activities for electrochemical applications. In addition, the designed system offers a motif to understand the structure-efficiency relationship from those amino-acid residue with proton buffer ability in natural photosynthesis.

Cs2Mg(H2C3N3S3)4·8H2O: An Excellent Birefringent Material with Giant Optical Anisotropy in π-Conjugated Trithiocyanurate.

The design of giant birefringence was performed by adjusting cations to make parallel and compact alignments of π-conjugated (HxC3N3S3)x-3, where x = 1 and 2) groups with large polarizability anisotropy. Finally, the first mixed alkali/alkali-earth-metal trithiocyanurates, A2B(H2C3N3S3)4·nH2O (A = K, Rb, Cs; B = Mg, Sr; n = 5-8, 12), were designed and synthesized successfully. Importantly, Cs2Mg(H2C3N3S3)4·8H2O (III) and K2Sr(H2C3N3S3)4·5H2O (IV) possess large birefringences of 0.580 and 0.194 at 800 nm, respectively, of III has the largest birefringence among all practical birefringent crystals, cyanurates, and hydroisocyanurates.

Composite poly(ethylene oxide)-based solid electrolyte with consecutive and fast ion transport channels constructed by upper-dimensional MIL-53(Al) nanofibers.

Novel structural designs for metal organic frameworks (MOFs) are expected to improve ion-transport behavior in composite solid electrolytes. Herein, upper-dimensional MIL-53(Al) nanofibers (MNFs, MIL-53 belongs to the MIL (Material Institute Lavoisier) group) with flower-like nanoflake structures have been designed and constructed via modified hydrothermal coordination. The optimized MNFs with high surface area and porosity can form abundant interfaces with poly(ethylene oxide) (PEO) matrix. The plasticization of MNFs to the PEO matrix will facilitate segmental movement of PEO chains to facilitate Li+ conduction. The unsaturated open metal centers of MNFs can effectively capture bis(trifluoromethanesulfonyl)imide anions (TFSI-) to deliver more free lithium ions for transfer. Moreover, the upper-dimensional nanofiber structure endows lithium ions with a long-range and consecutive transport pathway. The obtained composite solid electrolyte (MNFs@PEO) presents a high ionic conductivity of 4.1 × 10-4 S cm-1 and a great Li+ transference number of 0.4 at 60 °C. The electrolyte also exhibits a stable Li plating/stripping behavior over 1000 h at 0.1 mA cm-1 with inhibited Li dendrite growth. Furthermore, the Li/LiFePO4 and Li/LiNi0.8Mn0.1Co0.1O2 batteries with MNFs@PEO as electrolytes both display great cycling stabilities with high-capacity retention, indicating their potential applications in lithium metal batteries. The study will put forward new inspirations for designing advanced MOF-based composite solid electrolytes.

Engineering of heterointerface of ultrathin carbon nanosheet-supported CoN/MnO enhances oxygen electrocatalysis for rechargeable Zn-air batteries.

Designing bifunctional electrocatalysts with outstanding reactivity and durability towards the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has remained a long-term aim for metal-air batteries. Achieving the high level of fusion between two distinct metal components to form bifunctional catalysts with optimized heterointerfaces and well-defined morphology holds noteworthy implications in the enhancement of electrocatalytic activity yet challenging. Herein, the fabrication of numerous heterointerfaces of CoN/MnO is successfully realized within ultrathin carbon nanosheets via a feasible self-templating synthesis strategy. Experimental results and theoretic calculations verify that the interfacial electron transfer from CoN to MnO at the heterointerface engenders an ameliorated charge transfer velocity, finely tuned energy barriers concerning reaction intermediates and ultimately accelerated reaction kinetics. The as-prepared CoN/MnO@NC demonstrates exceptional bifunctional catalytic performance, excelling in both OER and ORR showcasing a low reversible overpotential of 0.69 V. Furthermore, rechargeable liquid and quasi-solid-state flexible Zn-air batteries employing CoN/MnO@NC as the air-cathode deliver remarkable endurance and elevated power density, registering values of 153 and 116 mW cm-2 respectively and exceeding Pt/C + RuO2 counterparts and those reported in literature. Deeply exploring the effect of electron-accumulated heterointerfaces on catalytic activity would contribute wisdom to the development of bifunctional electrocatalysts for rechargeable metal-air batteries.

Engineering Sb/Zn4(OH)6SO4·5H2O interfacial layer by in situ chemically reacting for stable Zn anode.

Rechargeable aqueous zinc ion batteries with abundant resources and high safety have gained extensive attention in energy storage technology. However, the cycle stability is largely limited by notorious Zn dendrite growth and water-induced interfacial side reactions. Here, a uniform and robust protection layer consisting of metal antimony (Sb) nanoparticles and micrometer-size sheets Zn4(OH)6SO4·5H2O (ZHS) is purposely designed to stabilize Zn anode via an in situ chemical reaction strategy. The two-phase protection layers (Sb/ZHS) induce a reinforcement effect on the Zn anode (Zn@Sb/ZHS). Specifically, Sb nanoparticles play the part of nucleation sites to facilitate uniform Zn plating and homogenize the electric field around the Zn surface. ZHS micrometer-size sheets possess sufficient electrolyte wettability, fast ion transfer kinetics, and anti-corrosion, thus guaranteeing uniform ion flux and inhibiting H2O decomposition. As expected, the symmetric Zn@Sb/ZHS//Zn@Sb/ZHS cells achieve a minimal voltage hysteresis and a reversible cycle of over 2000 h at 1 mA cm-2. By pairing with the MnO2 cathode, the full cell exhibits a significantly improved stability (∼94.17 % initial capacity after 1500 cycles). This study provides a new strategy to design artificial protection layers.

Ether-Water Co-Solvent Electrolytes Enhanced Vanadium Oxide Cathode Cyclic Behaviors for Zinc Batteries.

Vanadium-based compounds are fantastic cathodes for aqueous zinc metal batteries due to the high specific capacity and excellent rate capability. Nevertheless, the practical application has been hampered by the dissolution of vanadium in traditional aqueous electrolytes owing to the strong polarity of water molecules. Herein, we propose a hybrid electrolyte made of Zn(ClO4)2 salt in tetraethylene glycol dimethyl ether (G4) and H2O solvents to upgrade the cycle life of Zn//K0.486V2O5 battery. The G4 jointly solvates with Zn2+ ions and replaces a portion of the H2O molecules in the Zn2+ solvation sheath. It forms a strong bond with H2O, reducing its activity, and significantly inhibiting vanadium dissolution and water-induced parasitic reaction. Consequently, the optimized electrolyte with H2O and G4 volume ratio of 5 : 5 enhances the cycling stability of Zn//K0.486V2O5 battery, enabling it to reach up to 600 cycles. In addition, the battery demonstrates a satisfactory reversible capacity of 475.7 mAh g-1 and excellent rate performance attributed to the moderate ionic conductivity (28.8 mS cm-1) of the hybrid electrolyte. Last but not least, in the optimized electrolyte, the symmetric Zn//Zn cells deliver a long cycling performance of 400 h, while the asymmetric Zn//Cu cells shows a high average coulombic efficiency of 97.4 %.

Lewis acid Mg2+-doped cobalt phosphate nanosheets for enhanced electrocatalytic oxygen evolution reaction.

Cobalt-based materials are considered to be promising electrocatalysts for the oxygen evolution reaction (OER). However, their catalytic efficiencies are still limited by sluggish surface adsorption and high activation overpotentials. Herein, Lewis acid Mg2+-doped Co3(PO4)2 nanosheets were prepared through a simple two-step strategy for enhanced electrocatalytic oxygen evolution reaction. The Lewis acid Mg2+ dopants can increase the cobalt-oxygen covalency and thus facilitate the adsorption of oxygenated intermediates, charge transfer and the pre-oxidation of cobalt species during the OER.

Recycling of Zinc-Carbon Batteries into MnO/ZnO/C to Fabricate Sustainable Cathodes for Rechargeable Zinc-Ion Batteries.

Acidic zinc-carbon dry batteries have been widely used in life because of their low cost. However, a great quantity of used batteries is discarded as refuse, which not only wastes resources but also leads to environmental contamination. To reuse spent batteries on a large scale, this study concerns a simple, effective, and sustainable strategy to turn them into MnO/ZnO/C composites. After a conventional leaching treatment followed by pyrolysis, the rust cathode materials can be reduced to MnO/ZnO/C. When serving as a rechargeable zinc-ion battery cathode, this electrode provides a maximum reversible capacity of around 362 mAh g-1 MnO ) and a rate capability of 191 mAh g-1 MnO at a high current rate of 1.20 A g-1 . Furthermore, ZnO gradually dissolves in the electrolyte with the increase of discharge cycles, replenishing the Zn2+ content in the electrolyte and further enhancing cycling stability (98.02 % after 500 cycles). The device also exhibits a remarkable energy density of 336.37 Wh kg-1 , low self-discharge rate, and can efficiently power a LED panel. This strategy offers an economical and facile route to convert zinc-carbon battery waste into useful materials for aqueous rechargeable zinc ion batteries.

Simultaneous voltammetric determination of epinephrine and acetaminophen using a highly sensitive CoAl-OOH/reduced graphene oxide sensor in pharmaceutical samples and biological fluids.

For this study, three novel types of sensors comprised of CoAl-layered double oxyhydroxide (CoAl-LDH), CoAl-LDH/reduced graphene oxide (rGO), and CoAl-OOH/rGO nanosheets were successfully fabricated on glassy carbon electrodes (GCEs) and employed for the electrochemical detection of epinephrine (EP) and acetaminophen (AC). Interestingly, we found that the CoAl-OOH/rGO/GCE was more suitable for the determination of EP and AC in contrast to the CoAl-LDH and CoAl-OOH/rGO sensors. Differential pulse voltammetry results revealed that the CoAl-OOH/rGO/GCE delivered excellent electrocatalytic activity. The sensitivities and detection limits for the simultaneous measurement of EP and AC were 12.2 µA µM-1 cm-2, 0.023 µM L-1, and 4.87 µA µM-1 cm-2, 0.058 µM L-1, respectively. Especially, the as-obtained CoAl-OOH/rGO/GCE was successfully utilized for the detection in pharmaceutical samples and biological fluids with satisfactory results. Owing to its outstanding electrocatalytic activity and superior sensitivity, the CoAl-OOH/rGO/GCE could be beneficial to construct a promising electrochemical sensor for the detection of EP and AC.

Effects of gold nanoparticle morphologies on interactions with proteins.

In biological milieu, nanoparticles tend to bind with a variety of biomolecules, particularly proteins, thereby forming an interfacial corona that endows them with a new biological identity. A thorough understanding of these protein coronas is likely to provide insights into nanoparticle biodistribution and nanoparticle-mediated cytotoxicity, leading to the expansion of potential applications and the further elucidation of the biological impacts of nanoparticles in biomedical applications. Herein, three differently shaped AuNPs were synthesized, namely nanospheres (AuNSPs), nanorods (AuNRs), and nanostars (AuNSs). The effects of the morphologies of AuNPs on the structures and functions of adsorbed fibrinogen (FIB) and trypsin (Try) were investigated via circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR). Simultaneously, two different types of proteins were employed to investigate their influences on the stability and aggregation of AuNPs, using UV-vis absorption spectroscopy, transmission electron microscopy (TEM), microscale thermophoresis (MST), and dynamic light scattering (DLS). It was found that, compared to AuNSPs, the irregularly shaped AuNPs (e.g., AuNRs and AuNSs) had the capacity to induce greater changes in the secondary structures of the proteins. Furthermore, it appeared that the differently shaped AuNPs had obvious effects on the secondary structure of Try, and slight effects on the secondary structure of FIB. Consequently, these preliminary results indicated that the formation of protein corona, as well as the aggregation behaviors of the AuNPs was intimately related to the specific shapes of the AuNPs and the unique structures of the proteins.

Nitrogen-Doped Cobalt Pyrite Yolk-Shell Hollow Spheres for Long-Life Rechargeable Zn-Air Batteries.

Limited by the sluggish four-electron transfer process, designing high-performance nonprecious electrocatalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is urgently desired for efficient rechargeable Zn-air batteries (ZABs). Herein, the successful synthesis of porous nitrogen-doped cobalt pyrite yolk-shell nanospheres (N-CoS2 YSSs) is reported. Benefiting from the abundant porosity of the porous yolk-shell structure and unique electronic properties by nitrogen doping, the as-prepared N-CoS2 YSSs possess more exposed active surface, thus giving rise to superior activity for reversible oxygen electrocatalysis and outstanding cycling stability (more than 165 h at 10 mA cm-2) in ZABs, exceeding the commercial Pt/C and RuO2 hybrid catalysts. Moreover, the assembled ZABs, delivering a specific capacity of 640 mAh gZn -1, can be used for practical devices. This work provides a novel tactic to engineer sulfides as high efficiency and promising bifunctional oxygen electrocatalysts for advanced metal-air batteries.

Powder exfoliated MoS2 nanosheets with highly monolayer-rich structures as high-performance lithium-/sodium-ion-battery electrodes.

Due to their low yield and easy aggregation during the electrode preparation process, exfoliated MoS2 monolayers cannot fulfill the requirements of alkali-metal-ion battery tests. Hence, we have developed a facile process to fabricate powder exfoliated MoS2 nanosheets capable of large-scale production and having highly monolayer-rich structures. This process contains two steps: liquid-phase exfoliation of the edge-rich MoS2 precursor and a freeze-drying procedure. The proposed MoS2 precursors contain rich edge fractions that are easily exfoliated by this method, and the freeze-drying procedure can maintain the unique monolayer-rich structure of MoS2 in the powder phase. The electrochemical evaluations of both lithium- and sodium-ion batteries reveal that the proposed powder exfoliated monolayer-rich MoS2 electrode exhibits remarkable specific capacities and stable cyclic performances. In particular, the monolayer-rich MoS2 nanosheet electrode delivers a superior lithium-storage capacity of ∼1400 mA h g-1. The exfoliated MoS2 nanosheet electrode can withstand over 1000 cycles even at 1 A g-1. The mechanism reveals that these unique MoS2 nanosheets not only have a large surface area but also their inclusive monolayer structures exhibit much higher charge mobility than those of bulk MoS2.

A novel electrochemical sensor based on FeS anchored reduced graphene oxide nanosheets for simultaneous determination of dopamine and acetaminophen.

In this paper, FeS nanoparticles anchored on reduced graphene oxide (rGO) nanosheets are synthesized via a facile direct-precipitation method. For the first time, a novel electrochemical sensor is developed based on FeS/rGO nanosheets modified glassy carbon electrode (GCE). It has been proved that the resultant FeS/rGO/GCE sensor is very suitable for the individual and simultaneous measurement of dopamine (DA) and acetaminophen (AC) and delivers excellent anti-interference ability to ascorbic acid (AA) and uric acid (UA). Under optimum conditions with differential pulse voltammetry method, a broad linear response versus the concentrations of DA and AC has been observed in the ranges of 2.0 to 250.0µM and 5.0 to 300.0µM, respectively. The detection limits for DA and AC are 0.098µM and 0.18µM, respectively. Furthermore, the as-obtained sensor has been successfully utilized in real samples and satisfactory results have been achieved. Consequently, by virtue of its outstanding electrocatalytic activity, excellent sensitivity, and long time stability, the as-obtained FeS/rGO modified electrode can be considered as a new promising DA and AC sensor.