Dual-Ligand Strategy to Construct Metal Organic Gel Catalyst with the Optimized Electronic Structure for High-Efficiency Overall Water Splitting and Flexible Metal-Air Battery.

Non-noble metal catalysts are known for their efficient catalytic performance for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Metal organic gels (MOGs) can be considered as a promising electrocatalyst owing to the diverse physicochemical properties but usually suffer from its poor electrical conductivity and catalytic stability. Here, a FeCo-MOG is constructed with considerable trifunctional activity. The optimal P-CoFe-H3 prepared by using phytic acid (PA) and 2,4,6-Tris[(p-carboxyphenyl)amino]-1,3,5-triazine benzoic acid (H3TATAB) as dual ligands), exhibits outstanding ORR, OER, and HER activities as well as stability, exceeding most of state-of-the-art catalysts. As expected, the flexible Zn-air battery applied with P-CoFe-H3 as air cathode displays considerable power density, discharge voltage plateau, and cycling stability. Impressively, it is also capable of driving the overall water-splitting device by applying the P-CoFe-H3 as anode and cathode. Furthermore, theoretical calculations reveal that dual ligands can optimize the coordination environment and charge density of active sites, thereby reducing the absorption energy of intermediate species and boosting the catalytic performance. This work endows the dual-ligands coordination strategy with great potentiality for MOGs-based electrocatalysts in energy conversion devices.

High-Energy-Density Solid-State Metal-Air Batteries: Progress, Challenges, and Perspectives.

Next-generation batteries have long been considered a transition to more sustainable storage technologies. Among them, metal-air batteries (MABs) with low cost, high safety, and environmental friendliness have shown great potential for future large-scale applications. Motivated by the desirable characteristics, significant progress is made in suppressing serious parasitic reactions, improving electrochemical performance, and increasing the energy density in MABs. Compared to the widely reported liquid electrolyte strategy, solid-state electrolytes (SSEs) can thoroughly solve the volatilization challenges of liquid electrolytes and protect the oxygen electrodes without the formation of diffusion-blocking oxide phases. Notably, SSEs for MABs are still in their infancy, and many thorny challenges still need to be solved. In this review, the main electrochemical mechanism, key challenges, and some important progress are sorted out for solid-state MABs, such as lithium-air, zinc-air, aluminum-air, and magnesium-air batteries. Besides their fundamental significance, these configurations are further compared in terms of energy density, cost, carbon footprint, energy consumption, rate performance, cycle performance, safety, and air stability of prevailing electrolytes.

Power Scavenging Microsystem for Smart Contact Lenses.

On-the-eye microsystems such as smart contacts for vision correction, health monitoring, drug delivery, and displaying information represent a new emerging class of low-profile (≤ 1 mm) wireless microsystems that conform to the curvature of the eyeball surface. The implementation of suitable low-profile power sources for eye-based microsystems on curved substrates is a major technical challenge addressed in this paper. The fabrication and characterization of a hybrid energy generation unit composed of a flexible silicon solar cell and eye-blinking activated Mg-O2 metal-air harvester capable of sustainably supplying electrical power to smart ocular devices are reported. The encapsulated photovoltaic device provides a DC output with a power density of 42.4 µW cm-2 and 2.5 mW cm-2 under indoor and outdoor lighting conditions, respectively. The eye-blinking activated Mg-air harvester delivers pulsed power output with a maximum power density of 1.3 mW cm-2. A power management circuit with an integrated 11 mF supercapacitor is used to convert the harvesters' pulsed voltages to DC, boost up the voltages, and continuously deliver ≈150 µW at a stable 3.3 V DC output. Uniquely, in contrast to wireless power transfer, the power pack continuously generates electric power and does not require any type of external accessories for operation.

From lithium and sodium superoxides to singlet-oxygen - insights into the mechanism of dissociation using SHARC-MD.

The parasitic formation of singlet oxygen in aprotic alkaline/air batteries presents a challenge for the technical development of these systems. Avoidance strategies and investigation of reaction paths such as disproportionation of LiO2 and NaO2 have been presented. Furthermore, the dissociation of these superoxide systems have been discussed be as an alternative reaction channel. Here, we present a fundamental study of the electronic nature and dissociation behaviour of the alkali superoxides. The molecular systems were calculated at the CASSCF/CASPT2-level of theory. We determined the minimum energy crossing points along the dissociation required to form 3O2 and 1O2. Building on these results, a surface-hopping AIMD-simulation was performed employing the SHARC program package to follow the electronic transitions along the minimum energy crossing pooints during the dissociation. The feasibility of populating the electronic state corresponding to the formation of singlet oxygen during dissociation was demonstrated. For LiO2, 6.85% of the trajectories were found to terminate under formation of 1O2, whereas for NaO2 only 1.68% of the trajectories ended up in 1O2 formation. This represents an inverse trend to that reported in the literature. This observation suggests that the dissociation is a viable, monomolecular reaction path to 1O2 that complements the disproportionation pathway.

Silica-Derived Nanostructured Electrode Materials for ORR, OER, HER, CO2RR Electrocatalysis, and Energy Storage Applications: A Review.

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords "silica", "electrocatalysts", "ORR", "OER", "HER", "HOR", "CO2RR", "batteries", and "supercapacitors". The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

Engineering Energy Level of FeN4 Sites via Dual-Atom Site Construction Toward Efficient Oxygen Reduction.

Single-atom catalysts based on metal-N4 moieties and embedded in a graphite matrix (defined as MNC) are promising for oxygen reduction reaction (ORR). However, the performance of MNC catalysts is still far from satisfactory due to their imperfect adsorption energy to oxygen species. Herein, single-atom FeNC is leveraged as a model system and report an adjacent Ru-N4 moiety modulation effect to optimize the catalyst's electronic configuration and ORR performance. Theoretical simulations and physical characterizations reveal that the incorporation of Ru-N4 sites as the modulator can alter the d-band electronic energy of Fe center to weaken the FeO binding affinity, thus resulting in the lower adsorption energy of ORR intermediates at Fe sites. Thanks to the synergetic effects of neighboring Fe and Ru single-atom pairs, the FeN4 /RuN4 catalyst exhibits a half-wave potential of 0.958 V and negligible activity degradation after 10 000 cycles in 0.1 m KOH. Metal-air batteries using this catalyst in the cathode side exhibit a high power density of 219.5 mW cm-2 and excellent cycling stability for over 2370 h, outperforming the state-of-the-art catalysts.

Revealing Atomic Configuration and Synergistic Interaction of Single-Atom-Based Zn-Co-Fe Trimetallic Sites for Enhancing Oxygen Reduction and Evolution Reactions.

Anchoring single metal atom to carbon supports represents an exceptionally effective strategy to maximize the efficiency of catalysts. Recently, dual-atom catalysts (DACs) emerge as an intriguing candidate for atomic catalysts, which perform better than single-atom catalysts (SACs). However, the clarification of the polynary single-atom structures and their beneficial effects remains a daunting challenge. Here, atomically dispersed triple Zn-Co-Fe sites anchored to nitrogen-doped carbon (ZnCoFe-N-C) prepared by one-step pyrolysis of a designed metal-organic framework precursor are reported. The atomically isolated trimetallic configuration in ZnCoFe-N-C is identified by annular dark-field scanning transmission electron microscopy and spectroscopic techniques. Benefiting from the synergistic effect of trimetallic single atoms, nitrogen, and carbon, ZnCoFe-N-C exhibits excellent catalytic performance in bifunctional oxygen reduction/evolution reactions in an alkaline medium, outperforming other SACs and DACs. The ZnCoFe-N-C-based Zn-air battery exhibits a high specific capacity (liquid state: 931.8 Wh kgZn -1 ), power density (liquid state: 137.8 mW cm-2 ; all-solid-state: 107.9 mW cm-2 ), and good cycling stability. Furthermore, density-functional theory calculations rationalize the excellent performance by demonstrating that the ZnCoFe-N-C catalyst has upshifted d-band center that enhances the adsorption of the reaction intermediates.

Insights into the Electrochemical Behavior of Manganese Oxides as Catalysts for the Oxygen Reduction and Evolution Reactions: Monometallic Core-Shell Mn/Mn3 O4.

Overcoming the sluggish electrode kinetics of both oxygen reduction and evolution reactions (ORR/OER) with non-precious metal electrocatalysts will accelerate the development of rechargeable metal-air batteries and regenerative fuel cells. The authors investigated the electrochemical behavior and ORR/OER catalytic activity of core-porous shell Mn/Mn3 O4 nanoparticles in comparison with other manganese dioxides (ß- and γ-MnO2 ), and benchmarked against Pt/C and Pt/C-IrO2 . Under reversible operation in O2 -saturated 5 M KOH at 22 °C, the early stage activity of core-shell Mn/Mn3 O4 shows two times higher ORR and OER current density compared to the other MnO2 structures at 0.32 and 1.62 V versus RHE, respectively. It is revealed that Mn(III) oxidation to Mn(IV) is the primary cause of Mn/Mn3 O4 activity loss during ORR/OER potential cycling. To address it, an electrochemical activation method using Co(II) is proposed. By incorporating Co(II) into MnOx , new active sites are introduced and the content of Mn(II) is increased, which can stabilize the Mn(III) sites through comproportionation with Mn(IV). The Co-incorporated Mn/Mn3 O4 has superior activity and durability. Furthermore, it also surpassed the activity of Pt/C-IrO2 with similar durability. This study demonstrates that cost-effective ORR/OER catalysis is possible.

Photo-Assisted Metal-Air Batteries: Recent Progress, Challenges and Opportunities.

To meet the need of high energy density, long durability, safe and cost-efficient energy conversion and storage devices, metal-air batteries like Li-O2 and Zn-O2 batteries have received enormous attention and were subject to exciting development in the past decade. Photo-assisted strategies that enable the effective combination of photo/electric energy conversion/storage render a new dimension for the conventional metal-air batteries techniques with mere electric energy utilization. Therefore, tremendous research is ongoing in search of more efficient and durable devices with photo-assisted strategies. This review provides an overview of photo-assisted Li-O2 batteries, Zn-O2 batteries, and batteries with various metal/air components. The working mechanism, the basic device architecture and practical performances of various photo-assisted systems are summarized and discussed. Furthermore, certain technical challenges and future opportunities for the photo-assisted metal air batteries are emphasized and discussed in the hope of stimulating further research.

Biomass-Derived Carbon Materials for the Electrode of Metal-Air Batteries.

Facing the challenges of energy crisis and global warming, the development of renewable energy has received more and more attention. To offset the discontinuity of renewable energy, such as wind and solar energy, it is urgent to search for an excellent performance energy storage system to match them. Metal-air batteries (typical representative: Li-air battery and Zn-air battery) have broad prospects in the field of energy storage due to their high specific capacity and environmental friendliness. The drawbacks preventing the massive application of metal-air batteries are the poor reaction kinetics and high overpotential during the charging-discharging process, which can be alleviated by the application of an electrochemical catalyst and porous cathode. Biomass, also, as a renewable resource, plays a critical role in the preparation of carbon-based catalysts and porous cathode with excellent performance for metal-air batteries due to the inherent rich heteroatom and pore structure of biomass. In this paper, we have reviewed the latest progress in the creative preparation of porous cathode for the Li-air battery and Zn-air battery from biomass and summarized the effects of various biomass sources precursors on the composition, morphology and structure-activity relationship of cathode. This review will help us understand the relevant applications of biomass carbon in the field of metal-air batteries.

Smart Solar-Metal-Air Batteries Based on BiOCl Photocorrosion for Monolithic Solar Energy Conversion and Storage.

Herein, a BiOCl hydrogel film electrode featuring excellent photocorrosion and regeneration properties acts as the anode to construct a novel type of smart solar-metal-air batteries (SMABs), which combines the characteristics of solar cells (direct photovoltaic conversion) and metal-air batteries (electric energy storage and release interacting with atmosphere). The cyclic photocorrosion processes between BiOCl (Bi3+ ) and Bi can simply be achieved by solar light illumination and standing in the dark. Upon illumination, the device takes open-circuit configuration to charge itself from the sunlight. Notably, in this system, the converted solar energy can be stored in the SMABs without the need of external assistance. In the discharging process in the dark, Bi0 spontaneously turns back to Bi3+ producing electrons to induce the oxygen reduction reaction. With an illumination of 15 min, the battery with an electrode area of 1 cm2 can be continuously discharged for ≈3000 s. Taking elemental Bi as the calculation object, the theoretical capacity of the SMABs is 384.75 mAh g-1 , showing its potential application in energy storage. This novel type of SMABs is developed based on the unique photocorrosive and self-oxidation reaction of BiOCl to achieve photochemical energy generation and storage.

Light-Assisted Metal-Air Batteries: Progress, Challenges, and Perspectives.

Metal-air batteries are considered one of the most promising next-generation energy storage devices owing to their ultrahigh theoretical specific energy. However, sluggish cathode kinetics (O2 and CO2 reduction/evolution) result in large overpotentials and low round-trip efficiencies which seriously hinder their practical applications. Utilizing light to drive slow cathode processes has increasingly becoming a promising solution to this issue. Considering the rapid development and emerging issues of this field, this Review summarizes the current understanding of light-assisted metal-air batteries in terms of configurations and mechanisms, provides general design strategies and specific examples of photocathodes, systematically discusses the influence of light on batteries, and finally identifies existing gaps and future priorities for the development of practical light-assisted metal-air batteries.

MOF Structure Engineering to Synthesize CoNC Catalyst with Richer Accessible Active Sites for Enhanced Oxygen Reduction.

Single-atom cobalt-based CoNC are promising low-cost electrocatalysts for oxygen reduction reaction (ORR). However, further increasing the single cobalt-based active sites and the ORR activity remain a major challenge. Herein, an acetate (OAc) assisted metal-organic framework (MOF) structure-engineering strategy is developed to synthesize hierarchical accordion-like MOF with higher loading amount and better spatial isolation of Co and much higher yield when compared with widely reported polyhedron MOF. After pyrolysis, the accordion-structured CoNC (CoNC (A)) is loaded with denser CoN4 active sites (Co: 2.88 wt%), approximately twice that of Co in the CoNC reported. The presence of OAc in MOF also induces the generation of big pores (5-50 nm) for improving the accessibility of active sites and mass transfer during catalytic reactions. Consequently, the CoNC (A) catalyst shows an admirable ORR activity with a E1/2 of 0.89 V (40 mV better than Pt/C) in alkaline electrolytes, outstanding durability, and absolute tolerance to methanol in both alkaline and acidic media. The CoNC-based Zn-air battery exhibits a high specific capacity (976 mAh g-1 Zn ), power density (158 mW cm-2 ), rate capability, and long-term stability. This work demonstrates a reliable approach to construct single atom doped carbon catalysts with denser accessible active sites through MOF structure engineering.

Carbon Dots-Decorated Carbon-Based Metal-Free Catalysts for Electrochemical Energy Storage.

In the past ten years, carbon dots-decorated, carbon-based, metal-free catalysts (CDs-C-MFCs) have become the fastest-growing branch in the metal-free materials for energy storage field. However, the further development of CDs-C-MFCs needs to clear up the electronic transmission mechanism rather than primarily relying on trial-and-error approaches. This review presents systematically and comprehensively for the first time the latest advances of CDs-C-MFCs in supercapacitors and metal-air batteries. The structure-performance relationship of these materials is carefully discussed. It is indicated that carbon dots (CDs) can act as the electron-rich regions in CDs-C-MFCs owing to their unique properties, such as quantum confinement effects, abundant defects, countless functional groups, etc. More importantly, specific doping can effectively modify the charge/spin distribution and then facilitate electron transfer. In addition, present challenges and future prospects of the CDs-C-MFCs are also given.

Dual-Active Sites Engineering of N-Doped Hollow Carbon Nanocubes Confining Bimetal Alloys as Bifunctional Oxygen Electrocatalysts for Flexible Metal-Air Batteries.

Since the sluggish kinetic process of oxygen reduction (ORR)/evolution (OER) reactions, the design of highly-efficient, robust, and cost-effective catalysts for flexible metal-air batteries is desired but challenging. Herein, bimetallic nanoparticles encapsulated in the N-doped hollow carbon nanocubes (e.g., FeCo-NPs/NC, FeNi-NPs/NC, and CoNi-NPs/NC) are rationally designed via a general heat-treatment strategy of introducing NH3 pyrolysis of dopamine-coated metal-organic frameworks. Impressively, the resultant FeCo-NPs/NC hybrid exhibits superior bifunctional electrocatalytic performance for ORR/OER, manifesting exceptional discharging performance, outstanding lifespan, and prime flexibility for both Zn/Al-air batteries, superior to those of state-of-the-art Pt/C and RuO2 catalysts. X-ray absorption near edge structure and density functional theory indicate that the strong synergy between FeCo alloy and N-doped carbon frameworks has a distinctive activation effect on bimetallic Fe/Co atoms to synchronously modify the electronic structure and afford abundant dual-active Fe/Co-Nx sites, large surface area, high nitrogen doping level, and conductive carbon frameworks to boost the reversible oxygen electrocatalysis. Such N-doped carbon with bimetallic alloy bonds provides new pathways for the rational creation of high-efficiency energy conversion and storage equipment.

Stretchable Energy Storage Devices Based on Carbon Materials.

Stretchable energy storage devices are essential for developing stretchable electronics and have thus attracted extensive attention in a variety of fields including wearable devices and bioelectronics. Carbon materials, e.g., carbon nanotube and graphene, are widely investigated as electrode materials for energy storage devices due to their large specific surface areas and combined remarkable electrical and electrochemical properties. They can also be effectively composited with many other functional materials or designed into different microstructures for fabricating stretchable energy storage devices. This review summarizes recent advances toward the development of carbon-material-based stretchable energy storage devices. An overview of common carbon materials' fundamental properties and general strategies to enable the stretchability of carbon-material-based electrodes are presented. The performances of the as-fabricated stretchable energy storage devices including supercapacitors, lithium-ion batteries, metal-air batteries, and other batteries are then carefully discussed. Challenges and perspectives in this emerging field are finally highlighted for future studies.

Filling the Charge-Discharge Voltage Gap in Flexible Hybrid Zinc-Based Batteries by Utilizing a Pseudocapacitive Material.

The high charge-discharge voltage gap is one of the main bottlenecks of zinc-air batteries (ZABs) because of the kinetically sluggish oxygen reduction/evolution reactions (ORR/OER) on the oxygen electrode side. Thus, an efficient bifunctional catalyst for ORR and OER is highly desired. Herein, honeycomb-like MnCo2 O4.5 spheres were used as an efficient bifunctional electrocatalyst. It was demonstrated that both ORR and OER catalytic activity are promoted by MnIV -induced oxygen vacancy defects and multiple active sites. Importantly, the multivalent ions present in the material and its defect structure endow stable pseudocapacitance within the inactive region of ORR and OER; as a result, a low charge-discharge voltage gap (0.43 V at 10 mA cm-2 ) was achieved when it was employed in a flexible hybrid Zn-based battery. This mechanism provides unprecedented and valuable insights for the development of next-generation metal-air batteries.

Polymer-Assisted Electrophoretic Synthesis of N-Doped Graphene-Polypyrrole Demonstrating Oxygen Reduction with Excellent Methanol Crossover Impact and Durability.

The design and synthesis of metal-free catalysts with superior electrocatalytic activity, high durability, low cost, and under mild conditions is extremely desirable but remains challenging. To address this problem, a polymer-assisted electrochemical exfoliation technique of graphite in the presence of an aqueous acidic medium is reported. This simple, cost-effective, and mass-scale production approach could open the possibility for the synthesis of high-quality nitrogen-doped graphene-polypyrrole (NG-PPy). The NG-PPy catalyst displays an improved half wave potential (E1/2 =0.77 V) in alkaline medium compared with G-PPy (E1/2 =0.66 V). Most importantly, this catalyst demonstrates excellent stability with high methanol tolerance, and it outperforms the commercial Pt/C catalyst and other previously reported metal-free catalysts. The content of graphitic nitrogen atoms is the key factor for the enhancement of electrocatalytic activity towards oxygen reduction reactions (ORR). Interestingly, the NG-PPy catalyst can be used as a cathode material in a zinc-air battery, which demonstrates a higher peak power density (59 mW cm-2 ) than G-PPy (36.6 mW cm-2 ), highlighting the importance of the low-cost material synthesis approach towards the development of metal-free efficient ORR catalysts for fuel cell and metal-air battery applications. Remarkably, the polymer-assisted electrophoretic exfoliation of graphite with a high yield (≈88 wt %) of few-layer graphene flakes could pave the way towards the mass production of high-quality graphene for a variety of applications.

Generation of Nanoparticle, Atomic-Cluster, and Single-Atom Cobalt Catalysts from Zeolitic Imidazole Frameworks by Spatial Isolation and Their Use in Zinc-Air Batteries.

The size effect of transition-metal nanoparticles on electrocatalytic performance remains ambiguous especially when decreasing the size to the atomic level. Herein, we report the spatial isolation of cobalt species on the atomic scale, which was achieved by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo-ZIFs), and led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N-doped porous carbon. This synthetic strategy allowed an investigation of the size effect on electrochemical behavior from nanometer to Ångström dimensions. Single-atom Co catalysts showed superior bifunctional ORR/OER activity, durability, and reversibility in Zn-air batteries compared with the other derivatives and noble-metal Pt/C+RuO2 , which was attributed to the high reactivity and stability of isolated single Co atoms. Our findings open up a new avenue to regulate the metal particle size and catalytic performance of MOF derivatives.

Ultrahigh-Loading Zinc Single-Atom Catalyst for Highly Efficient Oxygen Reduction in Both Acidic and Alkaline Media.

Atomically dispersed Zn-N-C nanomaterials are promising platinum-free catalysts for the oxygen reduction reaction (ORR). However, the fabrication of Zn-N-C catalysts with a high Zn loading remains a formidable challenge owing to the high volatility of the Zn precursor during high-temperature annealing. Herein, we report that an atomically dispersed Zn-N-C catalyst with an ultrahigh Zn loading of 9.33 wt % could be successfully prepared by simply adopting a very low annealing rate of 1° min-1 . The Zn-N-C catalyst exhibited comparable ORR activity to that of Fe-N-C catalysts, and significantly better ORR stability than Fe-N-C catalysts in both acidic and alkaline media. Further experiments and DFT calculations demonstrated that the Zn-N-C catalyst was less susceptible to protonation than the corresponding Fe-N-C catalyst in an acidic medium. DFT calculations revealed that the Zn-N4 structure is more electrochemically stable than the Fe-N4 structure during the ORR process.