Wood-Structured Nanomaterials as Highly Efficient, Self-Standing Electrocatalysts for Water Splitting.

Electrocatalytic water splitting (EWS) driven by renewable energy is widely considered an environmentally friendly and sustainable approach for generating hydrogen (H2), an ideal energy carrier for the future. However, the efficiency and economic viability of large-scale water electrolysis depend on electrocatalysts that can efficiently accelerate the electrochemical reactions taking place at the two electrodes. Wood-derived nanomaterials are well-suited for serving as EWS catalysts because of their hierarchically porous structure with high surface area and low tortuosity, compositional tunability, cost-effectiveness, and self-standing integral electrode configuration. Here, recent advancements in the design and synthesis of wood-structured nanomaterials serving as advanced electrocatalysts for water splitting are summarized. First, the design principles and corresponding strategies toward highly effective wood-structured electrocatalysts (WSECs) are emphasized. Then, a comprehensive overview of current findings on WSECs, encompassing diverse structural designs and functionalities such as supported-metal nanoparticles (NPs), single-atom catalysts (SACs), metal compounds, and heterostructured electrocatalysts based on engineered wood hosts are presented. Subsequently, the application of these WSECs in various aspects of water splitting, including the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), overall water splitting (OWS), and hybrid water electrolysis (HWE) are explored. Finally, the prospects, challenges, and opportunities associated with the broad application of WSECs are briefly discussed. This review aims to provide a comprehensive understanding of the ongoing developments in water-splitting catalysts, along with outlining design principles for the future development of WSECs.

Copper nanodot-embedded nitrogen and fluorine co-doped porous carbon nanofibers as advanced electrocatalysts for rechargeable zinc-air batteries.

Porous carbon-based electrocatalysts for cathodes in zinc-air batteries (ZABs) are limited by their low catalytic activity and poor electronic conductivity, making it difficult for them to be quickly commercialized. To solve these problems of ZABs, copper nanodot-embedded N, F co-doped porous carbon nanofibers (CuNDs@NFPCNFs) are prepared to enhance the electronic conductivity and catalytic activity in this study. The CuNDs@NFPCNFs exhibit excellent oxygen reduction reaction (ORR) performance based on experimental and density functional theory (DFT) simulation results. The copper nanodots (CuNDs) and N, F co-doped carbon nanofibers (NFPCNFs) synergistically enhance the electrocatalytic activity. The CuNDs in the NFPCNFs also enhance the electronic conductivity to facilitate electron transfer during the ORR. The open porous structure of the NFPCNFs promotes the fast diffusion of dissolved oxygen and the formation of abundant gas-liquid-solid interfaces, leading to enhanced ORR activity. Finally, the CuNDs@NFPCNFs show excellent ORR performance, maintaining 92.5% of the catalytic activity after a long-term ORR test of 20000 s. The CuNDs@NFPCNFs also demonstrate super stable charge-discharge cycling for over 400 h, a high specific capacity of 771.3 mAh g-1 and an excellent power density of 204.9 mW cm-2 as a cathode electrode in ZABs. This work is expected to provide reference and guidance for research on the mechanism of action of metal nanodot-enhanced carbon materials for ORR electrocatalyst design.

Template-Mediated Synthesis of Hierarchically Porous Metal-Organic Frameworks for Efficient CO2/N2 Separation.

Carbon dioxide (CO2) is generally unavoidable during the production of fuel gases such as hydrogen (H2) from steam reformation and syngas composed of carbon monoxide (CO) and hydrogen (H2). Efficient separation of CO2 from these gases is highly important to improve the energetic utilization efficiency and prevent poisoning during specific applications. Metal-organic frameworks (MOFs), featuring ordered porous frameworks, high surface areas and tunable pore structures, are emerging porous materials utilized as solid adsorbents for efficient CO2 capture and separation. Furthermore, the construction of hierarchical MOFs with micropores and mesopores could further promote the dynamic separation processes, accelerating the diffusion of gas flow and exposing more adsorptive pore surface. Herein, we report a simple, efficient, one-pot template-mediated strategy to fabricate a hierarchically porous CuBTC (CuBTC-Water, BTC = 1,3,5-benzenetricarboxylate) for CO2 separation, which demonstrates abundant mesopores and the superb dynamic separation ability of CO2/N2. Therefore, CuBTC-Water demonstrated a CO2 uptake of 180.529 cm3 g-1 at 273 K and 1 bar, and 94.147 cm3 g-1 at 298 K and 1 bar, with selectivity for CO2/N2 mixtures as high as 56.547 at 273 K, much higher than microporous CuBTC. This work opens up a novel avenue to facilely fabricate hierarchically porous MOFs through one-pot synthesis for efficient dynamic CO2 separation.

A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode.

A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na3 V2 (PO4 )3 , Li3 V2 (PO4 )3 , K3 V2 (PO4 )3 , Na4 MnV(PO4 )3 , and Na2 TiV(PO4 )3 ) in a tetrahydrofuran/ethanol/H2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. The resulting hierarchically porous Na3 V2 (PO4 )3 possessing large specific surface area (≈77 m2 g-1 ) and pore volume (≈0.272 cm3 g-1 ) shows a high specific capacity of 117.6 mAh g-1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.

An oxidation-nitridation-denitridation approach to transform metal solids into foams with adjustable pore sizes for energy applications.

Metal foams with hierarchically porous structures are highly desirable in energy applications as active materials or their host substrates. However, conventional preparation methods usually have a quite limited flexibility of adjusting pore size of metal foams. Herein, an alternative new method based on gaseous thermal oxidation-nitridation-denitridation processes was developed to prepare metal (copper and nickel) foams with adjustable pore size by controlling the thermal nitridation temperature. Moreover, this environment-friendly method is independent of the shape of starting pure metal substrates and can be repeatedly applied to the metal substrates to create hierarchical porous structures containing different size pores. As a demonstration of the advantages of the resultant foams with abundant pores by this method, compared with its starting material (commercial Ni foam with the pore size of several millimeters), the resultant hierarchical porous Ni foam gives the remarkably enhanced performance of electrochemical water splitting as HER/OER electrodes and electrochemical energy storage as the host substrate of capacitive material MnO2. The metal foams with adjustable pore size prepared by the developed method will find a wide range of important applications in energy storage and conversion areas.

Crystalline Porous Organic Salts: From Micropore to Hierarchical Pores.

Crystalline porous organic salts (CPOSs), as an emerging class of porous organic materials, combining the uniform microporous system and distinct polarized channels, have become a highly evolving field of important current interest. The unique ionic bond of a CPOS endows the confined channels with high polarity, making CPOSs distinct from other organic frameworks. CPOSs show many fascinating properties, such as proton conductivity and fast transport of polar molecules, which involve the interaction between highly polarized guest molecules and host frameworks. Substantial progress has been made in the synthesis and applications of CPOSs. Herein, an overview is provided to impart a comprehensive understanding of the link between the synthetic approaches and the resultant microporous structure, the structure-function correlation and the state-of-the-art applications of CPOSs. The enhanced mass-transport performance of hierarchically porous structure in combination with the intrinsic polarized channels of CPOSs is very promising to create new applications and contribute to a new research upsurge. The perspective to construct porous hierarchy within the crystalline porous organic salts is assessed and will open a new research avenue. In the conclusion, the current challenges on the synthesis, structural regulation, and applications of CPOSs and the future of hierarchically porous crystalline organic salts are discussed.

General Approach to Produce Nanostructured Binary Transition Metal Selenides as High-Performance Sodium Ion Battery Anodes.

Multiple transition metals containing chalcogenides have recently drawn boosted attraction as anodes for sodium ion batteries (SIBs). Their greatly enhanced electrochemical performances can be attributed to the superior intrinsic conductivities and richer redox reactions, comparative to mono metal chalcogenides. To employ various binary metals comprising selenides (B-TMSs) for SIBs, discovery of a simplistic, scalable and universal synthesis approach is highly desirable. Herein, a simple, facile, and comprehensive strategy to produce various combinations of nanostructured B-TMSs is presented. As a proof of concept, optimized, high surface area bearing, and hierarchical nanosheets of iron-nickel selenide (FNSe), iron-cobalt selenide, and nickel-cobalt selenide are produced and employed in SIBs. These B-TMSs exhibit adequately high energy capacities, excellent rate capabilities, and an extraordinarily stable life of 2600 cycles. As far as it is known, it is the first work to discuss sodium storage of FNSe, so various in situ and ex situ battery analyses are carried out to probe the sodium storage mechanism. When employed in sodium full batteries, these B-TMSs present reasonably high reversible specific capacities even after 100 cycles. Overall, the presented strategy will pave the way for facile synthesis of numerous binary transition metal chalcogenides that are the potential materials for energy storage and conversion systems.

Hierarchically Porous Fe2 CoSe4 Binary-Metal Selenide for Extraordinary Rate Performance and Durable Anode of Sodium-Ion Batteries.

Owing to high energy capacities, transition metal chalcogenides have drawn significant research attention as the promising electrode materials for sodium-ion batteries (SIBs). However, limited cycle life and inferior rate capabilities still hinder their practical application. Improvement of the intrinsic conductivity by smart choice of elemental combination along with carbon coupling of the nanostructures may result in excellence of rate capability and prolonged cycling stability. Herein, a hierarchically porous binary transition metal selenide (Fe2 CoSe4 , termed as FCSe) nanomaterial with improved intrinsic conductivity was prepared through an exclusive methodology. The hierarchically porous structure, intimate nanoparticle-carbon matrix contact, and better intrinsic conductivity result in extraordinary electrochemical performance through their synergistic effect. The synthesized FCSe exhibits excellent rate capability (816.3 mA h g-1 at 0.5 A g-1 and 400.2 mA h g-1 at 32 A g-1 ), extended cycle life (350 mA h g-1 even after 5000 cycles at 4 A g-1 ), and adequately high energy capacity (614.5 mA h g-1 at 1 A g-1 after 100 cycles) as anode material for SIBs. When further combined with lab-made Na3 V2 (PO4 )3 /C cathode in Na-ion full cells, FCSe presents reasonably high and stable specific capacity.

Towards High-Performance Electrocatalysts for Oxygen Reduction: Inducing Atomic-Level Reconstruction of Fe-Nx Site for Atomically Dispersed Fe/N-Doped Hierarchically Porous Carbon.

A rational and effective strategy for the synthesis of a high-performance non-precious metal electrocatalyst for oxygen reduction reaction (ORR) was developed by inducing reconstruction of Fe-Nx site on pig-bone-derived nitrogen-doped hierarchically porous carbon. The resultant Fe/N-doped carbon electrocatalyst possessed abundant atomically dispersed non-planar Fe-N4 ORR active sites, with absolute presence of active D1 (FeII -N4 ) and D3 (N-FeII -N2+2 ) sites, as well as large specific surface area and three-dimensional porous structure with hierarchical micro-/meso-/macro-pore distribution, which increased the utilization of active sites and promoted mass transport of ORR reactants. This resulted in a remarkably superior ORR activity with half-wave potential of 0.87 V (20 mV higher than Pt/C) and kinetic current density of 10.9 mA cm-2 at 0.85 V (2.3-fold of Pt/C) in alkaline electrolyte. This methodology provides a route for atomic-level design of high-performance ORR electrocatalyst.

Free-Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li-O2 Batteries.

Free-standing macroporous air electrodes with enhanced interfacial contact, rapid mass transport, and tailored deposition space for large amounts of Li2 O2 are essential for improving the rate performance of Li-O2 batteries. An ordered mesoporous carbon membrane with continuous macroporous channels was prepared by inversely topological transformation from ZnO nanorod array. Utilized as a free-standing air cathode for Li-O2 battery, the hierarchically porous carbon membrane shows superior rate performance. However, the increased cross-sectional area of the continuous macropores on the cathode surface leads to a kinetic overpotential with large voltage hysteresis and linear voltage variation against Butler-Volmer behavior. The kinetics were investigated based on the rate-determining step of second electron transfer accompanied by migration of Li+ in solid or quasi-solid intermediates. These discoveries shed light on the design of the air cathode for Li-O2 batteries with high-rate performance.

Co-N Decorated Hierarchically Porous Graphene Aerogel for Efficient Oxygen Reduction Reaction in Acid.

Nitrogen-functionalized graphene materials have been demonstrated as promising electrocatalyst for the oxygen reduction reaction (ORR), owning to their respectable activity and excellent stability in alkaline electrolyte. However, they exhibit unacceptable catalytic activity in acid medium. Here, a hierarchically porous Co-N functionalized graphene aerogel is prepared as an efficient catalyst for the ORR in acid electrolyte. In the preparation process, polyaniline (PANI) is introduced as a pore-forming agent to aid in the self-assembly of graphene species into a porous aerogel networks, and a nitrogen precursor to induce in situ nitrogen doping. Therefore, a Co-N decorated graphene aerogel framework with a large surface area (485 m(2) g(-1)) and an abundance of meso/macropores is effectively formed after heat treatment. Such highly desired structures can not only expose sufficient active sites for the ORR but also guarantee the fast mass transfer in the catalytic process, which provides significant catalytic activity with positive onset and half wave potentials, low hydrogen peroxide yield, high resistance to methanol crossover, and remarkable stability that is comparable to commercial Pt/C in acid medium.

Sulfur, trace nitrogen and iron codoped hierarchically porous carbon foams as synergistic catalysts for oxygen reduction reaction.

Sulfur, trace nitrogen and iron codoped, hierarchically porous carbon foams (HPCFs) were fabricated by directly pyrolyzing sulfur-enriched conductive polymer, poly(3,4-ethylenedioxythiphene)-polystyrenesulfonic acid (PEDOT-PSS) aerogels under argon atmosphere. This simple pyrolysis treatment results in the molecular rearrangement of heteroatom sulfur, adjacent carbons and trace nitrogen/iron from oxidants to form active catalytic sites of HPCFs. At the same time, the high porosity of HPCFs provides the large surface area for the uniform distribution of active sites, and allows rapid oxygen transport and diffusion. As a result, these HPCFs exhibit the enhanced catalytic performances for oxygen reduction reaction (ORR) via a direct four-electron reduction pathway in alkaline electrolyte. Besides, they also display a higher stability and better methanol/CO tolerance than the commercial Pt/C catalyst, which makes them promising low cost, non-precious-metal ORR catalysts for practical application in fuel cells and metal-air batteries.

Hierarchically porous MnO2 microspheres doped with homogeneously distributed Fe3O4 nanoparticles for supercapacitors.

Hierarchically porous yet densely packed MnO2 microspheres doped with Fe3O4 nanoparticles are synthesized via a one-step and low-cost ultrasound assisted method. The scalable synthesis is based on Fe(2+) and ultrasound assisted nucleation and growth at a constant temperature in a range of 25-70 °C. Single-crystalline Fe3O4 particles of 3-5 nm in diameter are homogeneously distributed throughout the spheres and none are on the surface. A systematic optimization of reaction parameters results in isolated, porous, and uniform Fe3O4-MnO2 composite spheres. The spheres' average diameter is dependent on the temperature, and thus is controllable in a range of 0.7-1.28 µm. The involved growth mechanism is discussed. The specific capacitance is optimized at an Fe/Mn atomic ratio of r = 0.075 to be 448 F/g at a scan rate of 5 mV/s, which is nearly 1.5 times that of the extremely high reported value for MnO2 nanostructures (309 F/g). Especially, such a structure allows significantly improved stability at high charging rates. The composite has a capacitance of 367.4 F/g at a high scan rate of 100 mV/s, which is 82% of that at 5 mV/s. Also, it has an excellent cycling performance with a capacitance retention of 76% after 5000 charge/discharge cycles at 5 A/g.