Hierarchical Y and USY Zeolites Designed by Post‐Synthetic Strategies

Strategic combinations of affordable and scalable post‐synthetic modifications enabled to design a broad family of hierarchical Y and USY zeolites (FAU topology) independent on the Si/Al ratio. Pristine (Y, Si/Al = 2.4), steamed (USY, Si/Al = 2.6), and steamed and dealuminated (USY, Si/Al = 15 and 30) zeolites were exposed to a variety of acid (H₄EDTA and Na₂H₂EDTA) and base (NaOH) treatments, which led to the introduction of mesopore surfaces up to 500 m² g^?1, while preserving the intrinsic zeolite properties. Pristine Y and USY zeolites (Si/Al ～ 2.5) required mild dealumination (to Si/Al > 4 in the case of Y) to facilitate subsequent efficient desilication. Alkaline treatment of Y and USY zeolites with low Si/Al ratios (～4–6) led to an abundance of Al‐rich debris, which could be removed by a subsequent mild acid wash. On the other hand, severely steamed and dealuminated, hence Si‐rich, USY zeolites (Si/Al = 15 and 30) proved extremely sensitive to the alkaline solution, displaying facile dissolution and substantial amorphization. For the latter group of ultra‐stable Y zeolites, the presence of TPA⁺ in the alkaline solution enables to protect the zeolite structures upon the introduction of mesoporosity by desilication, preserving crystallinity and micropore volume. The sorption and catalytic properties of the hierarchical Y and USY zeolites were superior compared to the conventional counterparts.     

Hierarchical FAU‐ and LTA‐Type Zeolites by Post‐Synthetic Design: A New Generation of Highly Efficient Base Catalysts

Hierarchical FAU‐ and LTA‐type catalysts are prepared by post‐synthetic modifications and evaluated in the base‐catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. A novel route to attain mesoporous Al‐rich zeolites (A and X) is demonstrated, while mesoporous Y and USY zeolites are prepared using recently developed methods. Base functionality is introduced by alkali ion exchange (Cs, Na) or by high‐temperature nitridation in ammonia. A thorough characterization of the zeolites' structure, composition, porosity, morphology, and basicity demonstrates that the presence of a secondary mesopore network enhances the ion‐exchange efficiency and the structural incorporation of nitrogen. The modified USY zeolites display twice the conversion, while the hierarchical A, X, and Y are up to 10 times more active based on the enhanced accessibility. These results demonstrate that the Knoevenagel condensation takes place predominately at the external surface, highlighting secondary porosity as a key criterion in the design of basic zeolite catalysts.     

Beyond Creation of Mesoporosity: The Advantages of Polymer‐Based Dual‐Function Templates for Fabricating Hierarchical Zeolites

Direct synthesis of hierarchical zeolites currently relies on the use of surfactant‐based templates to produce mesoporosity by the random stacking of 2D zeolite sheets or the agglomeration of tiny zeolite grains. The benefits of using nonsurfactant polymers as dual‐function templates in the fabrication of hierarchical zeolites are demonstrated. First, the minimal intermolecular interactions of nonsurfactant polymers impose little interference on the crystallization of zeolites, favoring the formation of 3D continuous zeolite frameworks with a long‐range order. Second, the mutual interpenetration of the polymer and the zeolite networks renders disordered but highly interconnected mesopores in zeolite crystals. These two factors allow for the synthesis of single‐crystalline, mesoporous zeolites of varied compositions and framework types. A representative example, hierarchial aluminosilicate (meso‐ZSM‐5), has been carefully characterized. It has a unique branched fibrous structure, and far outperforms bulk aluminosilicate (ZSM‐5) as a catalyst in two model reactions: conversion of methanol to aromatics and catalytic cracking of canola oil. Third, extra functional groups in the polymer template can be utilized to incorporate desired functionalities into hierarchical zeolites. Last and most importantly, polymer‐based templates permit heterogeneous nucleation and growth of mesoporous zeolites on existing surfaces, forming a continuous zeolitic layer. In a proof‐of‐concept experiment, unprecedented core–shell‐structured hierarchical zeolites are synthesized by coating mesoporous zeolites on the surfaces of bulk zeolites.     

Novel Three Dimensional Cubic Fm3m Mesoporous Aluminosilicates with Tailored Cage Type Pore Structure and High Aluminum Content

Novel three dimensional cubic Fm3m mesoporous aluminosilicates (AlKIT‐5) with very high structural order and unprecedented loadings of Al in the silica framework have been successfully prepared for the first time by using non ionic surfactant as a template in a highly acidic medium. The obtained materials have been unambiguously characterized in detail by several sophisticated techniques such as XRD, N₂ adsorption, HRTEM, HRSEM, EDS, elemental mapping, ²⁷Al MAS NMR, and NH₃‐TPD. We also demonstrate that the nature, and the amount of Al incorporation in the silica framework can easily be controlled by simply varying the n_H2O/n_HCl and the n_Si/n_Al ratios, and the Al sources in the synthesis gel. Among the Al sources examined, the Al isopropoxide (AiPr) is superior over other Al sources. ²⁷Al MAS NMR results reveal that the amount of tetrahedral Al in the framework can be controlled by simply adjusting the n_Si/n_Al ratio in the synthesis gel, which increases with increasing the Al incorporation. One of the interesting findings in the work is the increase of the specific surface area, specific pore volume and the pore diameter of AlKIT‐5 with increasing the Al incorporation in the silica framework (up to n_Si/n_Al ratio of 10) while retaining the well‐ordered three dimensional cage type porous structure, and the mechanism for the unusual behavior has been discussed in detail. Finally, the acidity and the catalytic activity in the acetylation of veratrole of the AlKIT‐5 catalysts have been studied and the results have been compared with the several zeolites catalysts. Among the catalysts examined, AlKIT‐5(10) is found to be superior over the zeolites catalysts such as mordenite, zeolite H‐Y, zeolite H‐β, and ZSM‐5.     

Attractive In Situ Self‐Reconstructed Hierarchical Gradient Structure of Metallic Glass for High Efficiency and Remarkable Stability in Catalytic Performance

Metallic glass (MG), with the superiorities of unique disordered atomic structure and intrinsic chemical heterogeneity, is a new promising and competitive member in the family of environmental catalysts. However, what is at stake for MG catalysts is that their high catalytic efficiency is always accompanied by low stability and the disordered atomic configurations, as well as the structural evolution, related to catalytic performance, which raises a primary obstacle for their widespread applications. Herein, a non‐noble and multicomponent Fe₈₃Si₂B₁₁P₃C₁ MG catalyst that presents a fascinating catalytic efficiency while maintaining remarkable stability for wastewater remediation is developed. Results indicate that the excellent efficiency of the MG catalysts is ascribed to a unique atomic coordination that causes an electronic delocalization with an enhanced electron transfer. More importantly, the in situ self‐reconstructed hierarchical gradient structure, which comprises a top porous sponge layer and a thin amorphous oxide interfacial layer encapsulating the MG surface, provides matrix protection together with high permeability and more active sites. This work uncovers a new strategy for designing high‐performance non‐noble metallic catalysts with respect to structural evolution and alteration of electronic properties, establishing a solid foundation in widespread catalytic applications.     

Ag Anchored Atomically Around Nanopores of Porous Co(OH)2 for Efficient Bifunctional Oxygen Catalysis

Various clean energy storage and conversion systems highly depend on rational design of efficient electrocatalysts for oxygen reactions. Increasing both gas molecular diffusion and intrinsic activity is critical to boosting its efficiency for bifunctional oxygen electrocatalysis. However, controllable synthesis of catalysts that combines gas molecular diffusion and intrinsic activity remains a fundamental challenge. Herein, a two-step synthetic strategy is adopted to fabricate a composite oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional catalyst (P-Ag-Co(OH)₂), of which, atomic Ag is anchored in reactive oxygen atoms around nanopores of Co(OH)₂ nanosheets. Abundant nanopores provide enough gas molecular diffusion channels, and the special Ag-O-Co-OH catalytic groups around nanopores display high intrinsic catalytic activity, which jointly result in an excellent ORR/OER performance. In alkaline electrolyte, P-Ag-Co(OH)₂ displays a high half-wave potential (0.902 V versus RHE) for ORR, and a low overpotential (235 mV at 10 mA cm⁻²) for OER, which is superior to non-noble catalysts in previous studies and Pt/C (Ir/C) catalyst. At the same time, the single-cell zinc-air battery is prepared with an extremely high discharge peak power density of 435 mW cm⁻² and excellent discharge–charge cycle stability.     

Electro‐Oxidation of Ni42 Steel: A Highly Active Bifunctional Electrocatalyst

Janus type water‐splitting catalysts have attracted highest attention as a tool of choice for solar to fuel conversion. AISI Ni42 steel is upon harsh anodization converted into a bifunctional electrocatalyst. Oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are highly efficiently and steadfast catalyzed at pH 7, 13, 14, 14.6 (OER) and at pH 0, 1, 13, 14, 14.6 (HER), respectively. The current density taken from long‐term OER measurements in pH 7 buffer solution upon the electro‐activated steel at 491 mV overpotential (η) is around four times higher (4 mA cm^?2) in comparison with recently developed OER electrocatalysts. The very strong voltage–current behavior of the catalyst shown in OER polarization experiments at both pH 7 and at pH 13 are even superior to those known for IrO₂‐RuO₂. No degradation of the catalyst is detected even when conditions close to standard industrial operations are applied to the catalyst. A stable Ni‐, Fe‐oxide based passivating layer sufficiently protects the bare metal for further oxidation. Quantitative charge to oxygen (OER) and charge to hydrogen (HER) conversion are confirmed. High‐resolution XPS spectra show that most likely γ?NiO(OH) and FeO(OH) are the catalytic active OER and NiO is the catalytic active HER species.     

Interplay of Properties and Functions upon Introduction of Mesoporosity in ITQ‐4 Zeolite

The introduction of mesoporosity in zeolites is often directly coupled to changes in their overall catalytic performance without the detailed assessment of other key functions required for the rational design of the catalytic process such as accessibility, adsorption, and transport. This study presents an integrated approach to study property–function relationships in hierarchical zeolites. Accordingly, desilication of the 1D ITQ‐4 zeolite in alkaline medium is applied to develop different degrees of mesoporosity. Along with porosity modification, significant changes in composition, structure, and acidity occur. Relationships are established between the physicochemical properties of the zeolites and their characteristics in the adsorption and elution of light hydrocarbons (C₂ to C₅, alkanes and alkenes) as well as in the catalytic activity in low‐density polyethylene (LDPE) pyrolysis. The recently introduced hierarchy factor can appropriately relate porosity changes to catalytic performance.     

Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.     

Zeolite Catalysts with Tunable Hierarchy Factor by Pore‐Growth Moderators

The design of hierarchical zeolite catalysts is attempted through the maximization of the hierarchy factor (HF); that is, by enhancing the mesopore surface area without severe penalization of the micropore volume. For this purpose, a novel desilication variant involving NaOH treatment of ZSM‐5 in the presence of quaternary ammonium cations is developed. The organic cation (TPA⁺ or TBA⁺) acts as a pore‐growth moderator in the crystal by OH^?‐assisted silicon extraction, largely protecting the zeolite crystal during the demetallation process. The protective effect is not seen when using cations that are able to enter the micropores, such as TMA⁺ Engineering the pore structure at the micro‐ and mesolevel is essential to optimize transport properties and catalytic performance, as demonstrated in the benzene alkylation with ethylene, a representative mass‐transfer limited reaction. The hierarchy factor is an appropriate tool to classify hierarchically structured materials. The latter point is of wide interest to the scientific community as it not only embraces mesoporous zeolites obtained by desilication methods but it also enables to quantitatively compare and correlate various materials obtained by different synthetic methodologies.     

Ru Species Supported on MOF‐Derived N‐Doped TiO2/C Hybrids as Efficient Electrocatalytic/Photocatalytic Hydrogen Evolution Reaction Catalysts

The development of efficient catalysts is of great importance for hydrogen evolution reaction (HER) of water splitting via electrocatalytic/photocatalytic processes to remediate the current severe environmental and energy problems. By aid of the stabilization effects of uncoordinated groups and inherent pore‐confinement of amine‐functionalized metal–organic frameworks (NH₂‐MIL‐125), two forms of Ru species including nanoparticles (NPs) and/or single atoms (SAs) can be firmly embedded in NH₂‐MIL‐125 derived N‐doped TiO₂/C support (N‐TC), and thus obtain two kinds of samples named Ru‐NPs/SAs@N‐TC and Ru‐SAs@N‐TC, respectively. In the synthetic process, the initial feeding amount of Ru³⁺ ions not only strongly determines the final size and dispersion states of Ru species but also the morphology and defective structures of N‐TC support. Impressively, Ru‐NPs/SAs@N‐TC exhibit superior catalytic activities to Ru‐SAs@N‐TC for either electrocatalytic or photocatalytic HER. This should be attributed to its larger specific surface area and benefiting from synergistic coupling of Ru NPs and Ru SAs. It is envisioned that the present work can provide a new avenue for development of high‐efficiency and multifunctional hybrid catalysts in sustainable energy conversion.     

Mechanistic Insights on Ternary Ni2−xCoxP for Hydrogen Evolution and Their Hybrids with Graphene as Highly Efficient and Robust Catalysts for Overall Water Splitting

Searching the high‐efficient, stable, and earth‐abundant electrocatalysts to replace the precious noble metals holds the promise for practical utilizations of hydrogen and oxygen evolution reactions (HER and OER). Here, a series of highly active and robust Co‐doped nickel phosphides (Ni_2?xCo_xP) catalysts and their hybrids with reduced graphene oxide (rGO) are developed as bifunctional catalysts for both HER and OER. The Co‐doping in Ni₂P and their hybridization with rGO effectively regulate the catalytic activity of the surface active sites, accelerate the charge transfer, and boost their superior catalytic activity. Density functional theory calculations show that the Co‐doped catalysts deliver the moderate trapping of atomic hydrogen and facile desorption of the generated H₂ due to the H‐poisoned surface active sites of Ni_2?xCo_xP under the real catalytic process. Electrochemical measurements reveal the high HER efficiency and durability of the NiCoP/rGO hybrids in electrolytes with pH 0–14. Coupled with the remarkable and robust OER activity of the NiCoP/rGO hybrids, the practical utilization of the NiCoP/rGO‖NiCoP/rGO for overall water splitting yields a catalytic current density of 10 mA cm^?2 at 1.59 V over 75 h without an obvious degradation and Faradic efficiency of ≈100% in a two‐electrode configuration and 1.0 m KOH.     

Metal Ion‐Terpyridine‐Functionalized L‐Tyrosinamide Aptamers: Nucleoapzymes for Oxygen Insertion into C?H Bonds and the Transformation of L‐Tyrosinamide into Amidodopachrome

A series of metal ion‐terpyridine‐modified L‐tyrosinamide aptamers (M^{n +} = Cu²⁺ or Fe³⁺) act as enzyme‐mimicking catalysts (nucleoapzymes) for oxygen‐insertion into C? H bonds and the transformation of L‐tyrosinamide into amidodopachrome. The reaction proceeds in the presence of H₂O₂ and coadded L‐ascorbic acid. In one series of experiments, the catalyzed oxidation of L‐tyrosinamide to amidodopachrome by a set of nucleoapzymes consisting of Fe³⁺‐ or Cu²⁺‐terpyridine complexes tethered directly or through a 4 × thymidine (4 × T) bridge, to the 5′‐ or 3′‐end of the 49‐mer L‐tyrosinamide aptamer or to a shorter 23‐mer L‐tyrosinamide aptamer is examined. All nucleoapzymes reveal catalytic Michaelis–Menten enzyme‐like activities and the separated Fe³⁺‐ or Cu²⁺‐terpyridine and L‐tyrosinamide aptamer units show only minute catalytic properties. The catalytic activities of the nucleoapzymes are attributed to the concentration of the L‐tyrosinamide substrate by the aptamer units in proximity to the catalytic sites (K_d = (14 ± 0.1) × 10^?6 m for all 49‐mer catalysts and K_d = (2.5 ± 0.1) × 10^?6 m and K_d = (0.8 ± 0.04) × 10^?6 m for the 23‐mer catalysts). Electron spin resonance experiments reveal that ?OH radicals and ascorbate radicals participate in the transformation of tyrosine derivatives to catechol products. An autocatalytic feedback mechanism for the amplified generation of the two radicals is suggested.     

Mesoporous Carbon Nanocube Architecture for High‐Performance Lithium–Oxygen Batteries

One of the major challenges to develop high‐performance lithium–oxygen (Li–O₂) battery is to find effective cathode catalysts and design porous architecture for the promotion of both oxygen reduction reactions and oxygen evolution reactions. Herein, the synthesis of mesoporous carbon nanocubes as a new cathode nanoarchitecture for Li–O₂ batteries is reported. The oxygen electrodes made of mesoporous carbon nanocubes contain numerously hierarchical mesopores and macropores, which can facilitate oxygen diffusion and electrolyte impregnation throughout the electrode, and provide sufficient spaces to accommodate insoluble discharge products. When they are applied as cathode catalysts, the Li–O₂ cells deliver discharge capacities of 26 100 mA h g^?1 at 200 mA g^?1, which is much higher than that of commercial carbon black catalysts. Furthermore, the mesoporous nanocube architecture can also serve as a conductive host structure for other highly efficient catalysts. For instance, the Ru functionalized mesoporous carbon nanocubes show excellent catalytic activities toward oxygen evolution reactions. Li–O₂ batteries with Ru functionalized mesoporous carbon nanocube catalysts demonstrate a high charge/discharge electrical energy efficiency of 86.2% at 200 mA g^?1 under voltage limitation and a good cycling performance up to 120 cycles at 400 mA g^?1 with the curtaining capacity of 1000 mA h g^?1.     

NiCo Alloy Nanoparticles Decorated on N‐Doped Carbon Nanofibers as Highly Active and Durable Oxygen Electrocatalyst

The exploring of catalysts with high‐efficiency and low‐cost for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key issues for many renewable energy systems including fuel cells, metal–air batteries, and water splitting. Despite several decades pursuing, bifunctional oxygen catalysts with high catalytic performance at low‐cost, especially the one that could be easily scaled up for mass production are still missing and highly desired. Herein, a hybrid catalyst with NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers is synthesized by a facile electrospinning method and postcalcination treatment. The hybrid catalyst NiCo@N‐C 2 exhibits outstanding ORR and OER catalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO₂ catalysts, respectively. The synergetic effects between alloy nanoparticles and the N‐doped carbon fiber are considered as the main contributions for the excellent catalytic activities, which include decreasing the intrinsic and charge transfer resistances, increasing C?C, graphitic‐N/pyridinic‐N contents in the hybrid catalyst. This work opens up a new way to fabricate high‐efficient, low‐cost oxygen catalysts with high production.     

Tailored Mesoporosity Development in Zeolite Crystals by Partial Detemplation and Desilication

Partial detemplation of zeolites followed by desilication in alkaline medium is demonstrated as a powerful and elegant approach to design hierarchical zeolites with tailored degree of mesoporosity. This achievement, illustrated for large beta crystals, is based on the fact that the template‐containing zeolite is virtually inert to Si leaching upon treatment in aqueous NaOH solutions. Partial removal of the structure‐directing agent creates regions in the crystal susceptible to mesopore formation by subsequent desilication, while template‐containing regions are protected from silicon extraction. Variation of the calcination temperature in the range 230–550 °C determines the amount of template removed and enables control of the extent of mesopore formation in the zeolite (20–230 m² g^?1) upon alkaline treatment. The functionality of the introduced mesoporosity in the hierarchical beta crystals is demonstrated by the improved performance in the catalytic pyrolysis of low‐density polyethylene. The partial detemplation–desilication treatment enhances the tuning options of this demetallation method.     

High‐Quality Cuboid CH3NH3PbI3 Single Crystals for High Performance X‐Ray and Photon Detectors

Organic–inorganic halide hybrid perovskite materials are promising materials for X‐ray and photon detection due to their superior optoelectronic properties. Single‐crystal (SGC) perovskites have increasingly attracted attention due to their substantially low crystal defects, which contribute to improving the figures of merit of the devices. Cuboid CH₃NH₃PbI₃ SGC with the naturally favorable geometry for device fabrication is rarely reported in X‐ray and photon detection application. The concept of seed dissolution‐regrowth to improve crystal quality of cuboid CH₃NH₃PbI₃ SGC is proposed and a fundamental understanding of the nucleation and growth is provided thermodynamically. The X‐ray detector fabricated from cuboid CH₃NH₃PbI₃ SGC demonstrates the firstly reported high sensitivity of 968.9 µC^?1 Gy^?1 cm^?2 under ?1 V bias. The results also show that the favorable crystal orientation and high quality of cuboid CH₃NH₃PbI₃ leads to better responsivity and faster response speed than the more common dodecahedral CH₃NH₃PbI₃ in photodetection. Consequently, the work paves a way to synthesize high‐quality perovskite SGCs and benefits the application of MAPbI₃ SGCs with preferred crystal orientation and favorable crystal geometry for emerging device applications.     

Metal Nanocrystal‐Embedded Hollow Mesoporous TiO2 and ZrO2 Microspheres Prepared with Polystyrene Nanospheres as Carriers and Templates

Noble metal nanocrystals with different shapes and compositions are embedded in hollow mesoporous metal oxide microspheres through an ultrasonic aerosol spray. Polystyrene (PS) nanospheres are employed simultaneously as a hard template to create hollow interiors inside the oxide microspheres and as the carrier to bring pregrown metal nanocrystals, including Pd nanocubes, Au nanorods, and Au core/Pd shell nanorods, into the oxide microspheres. Calcination removes the PS template and causes the metal nanocrystals to adsorb on the inner surface of the hollow oxide microspheres. The catalytic performances of the Pd nanocube‐embedded TiO₂ and ZrO₂ microspheres are investigated using the reduction of 4‐nitrophenol as a model reaction. The presence of the mesopores in the oxide microspheres allows the reactant molecules to diffuse into the hollow interiors and subsequently interact with the Pd nanocubes. The embedding of the metal nanocrystals in the hollow oxide microspheres prevents the aggregation of the metal nanocrystals and reduces the loss of the catalyst during recycling. The Pd nanocube‐embedded ZrO₂ microspheres are found to exhibit a much higher catalytic activity, a much larger catalytic reaction rate, and a superior recyclability in comparison with a commercial Pd/C catalyst. This preparation approach could potentially be utilized to incorporate various types of mono‐ and multimetallic nanocrystals with different sizes, shapes, and compositions into hollow mesoporous oxide microspheres. Such a capability can facilitate the studies of the catalytic properties of various combinations of metal nanocrystals and metal oxide supports and therefore guide the design and creation of high‐performance catalysts.     

Autogenous Growth of Hierarchical NiFe(OH)x/FeS Nanosheet‐On‐Microsheet Arrays for Synergistically Enhanced High‐Output Water Oxidation

Practical electrochemical water splitting requires cost‐effective electrodes capable of steadily working at high output, leading to the challenges for efficient and stable electrodes for the oxygen evolution reaction (OER). Herein, by simply using conductive FeS microsheet arrays vertically pre‐grown on iron foam (FeS/IF) as both substrate and source to in situ form vertically aligned NiFe(OH)_x nanosheets arrays, a hierarchical electrode with a nano/micro sheet‐on‐sheet structure (NiFe(OH)_x/FeS/IF) can be readily achieved to meet the requirements. Such hierarchical electrode architecture with a superhydrophilic surface also allows for prompt gas release even at high output. As a result, NiFe(OH)_x/FeS/IF exhibits superior OER activity with an overpotential of 245 mV at 50 mA cm^?2 and can steadily output 1000 mA cm^?2 at a low overpotential of 332 mV. The water‐alkali electrolyzer using NiFe(OH)_x/FeS/IF as the anode can deliver 10 mA cm^?2 at 1.50 V and steadily operate at 300 mA cm^?2 with a small cell voltage for 70 h. Furthermore, a solar‐driven electrolyzer using the developed electrode demonstrates an exceptionally high solar‐to‐hydrogen efficiency of 18.6%. Such performance together with low‐cost Fe‐based materials and facile mass production suggest the present strategy may open up opportunities for rationally designing hierarchical electrocatalysts for practical water splitting or diverse applications.