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Physical field modulation has been regarded as a promising approach to boost the performance of various electrocatalysts and has recently received notable attention. However, such a technique by coupling an external field to controllably enable efficient and green electrosynthesis of hydrogen peroxide H2O2 through a 2e amp; 8722; oxygen reduction reaction ORR has not been perceived so far. In order to address the feasibility of this method, a controllable piezoelectric strategy based on the response of intrinsic electric domains to the stimulation of fluid mechanical force was exploited effectively to induce local electric fields on the polarized ceramic catalyst surface during the dynamic ORR. By adjusting the polarization degree of ceramic catalysts, the strength of the local electric field could be accordingly modulated, thus tuning the coverage of OH amp; 8722; ions on the catalyst surface which is beneficial for optimizing the binding strength towards oxygen containing intermediates and alleviating the disproportionation of the peroxide product

Cobalt‐iron oxyhydroxides (CoFeOOHx) are among the most active catalysts for the oxygen evolution reaction (OER). However, their redox behavior and the electronic and chemical structure of their active sites are still ambiguous. To shed more light on this, the complete and rapid reconstruction of four helical cobalt‐iron borophosphates with different Co:Fe ratios into disordered cobalt‐iron oxyhydroxides can be achieved, which are electrolyte‐penetrable and thus most transition metal sites can potentially participate in the OER. To track the redox behavior and to identify the active structure, quasi in situ X‐ray absorption spectroscopy is applied. Iron in high oxidation states ≥ IV (Fe4+) and its substantial redox behavior with an average oxidation state of around 2.8 to above 3.2 is detected. Furthermore, a 6% contraction of the Fe‐O bond length compared to Fe3+OOH references is observed during OER and a strong distortion of the [MO6] octahedra is identified. It is hypothesized that this bond contraction is caused by the presence of oxyl radicals and that di‐µ‐oxyl radical bridged cobalt‐iron centers are the active sites. It is anticipated that the detailed electronic and structural description can substantially contribute to the debate on the nature of the active site in bimetallic iron‐containing OER catalysts.

A hydrogen processing strategy is developed to enable bulk LaNi5 to attain high activity and long‐term stability toward the electrocatalytic oxygen evolution reaction (OER). By a combination of in situ Raman and quasi in situ X‐ray absorption (XAS) spectra, secondary‐electron‐excited scanning transmission electron microscopy (STEM) patterns as well as the Rietveld method and density functional theory (DFT) calculations, it is discovered that hydrogen‐induced lattice distortion, grain refinement, and particle cracks dictate the effective reconstruction of the LaNi5 surface into a porous hetero‐nanoarchitecture composed of uniformly confined active γ‐NiOOH nanocrystals by La(OH)3 layer in the alkaline OER process. This significantly optimizes the charge transfer, structural integrity, active‐site exposure, and adsorption energy toward the reaction intermediates. Benefiting from these merits, the overpotential (322 mV) at 100 mA cm−2 for the hydrogen‐processed OER catalyst deposited on nickel foam is reduced by 104 mV as compared to the original phase. Notably, it exhibits remarkable stability for 10 days at an industrial‐grade current density of more than 560 mA cm−2 in alkaline media.

Metal-organic frameworks (MOFs) are regarded as one promising class of precatalysts for electrocatalytic oxygen evolution reaction (OER), yet most of them suffer from poor conductivity and lack of coordinatively unsaturated metal sites, which hinders the fast electrochemical reconstruction and thus a poor OER activity. To address this issue, a unique heterocomposite has been constructed by in situ inserting carbon dots (CDs) into cobalt-based zeolitic imidazolate framework (Co-ZIF) nanosheet arrays (Co-ZIF/CDs/CC) in the presence of carbon cloth (CC) via one-pot coprecipitation for alkaline OER. Benefiting from the synergism between CDs and Co-ZIF subunits such as superior conductivity, strong charge interaction as well as abundant metal sites exposure, the Co-ZIF/CDs/CC exhibits an enhanced promotion effect for OER and contributes to the deep phase transformation from CDs-coupled Co-ZIF to CDs-coupled active CoOOH. As expected, the achieved Co-ZIF/CDs/CC only requires an overpotential of 226 mV to deliver 10 mA cm

Nanocrystalline or amorphous cobalt oxyhydroxides (CoCat) are promising electrocatalysts for the oxygen evolution reaction (OER). While having the same short range order, CoCat phases possess different electrocatalytic properties. This phenomenon is not conclusively understood, as multiple interdependent parameters affect the OER activity simultaneously. Herein, a layered cobalt borophosphate precatalyst, Co(H2O)2[B2P2O8(OH)2]∙H2O, is fully reconstructed into two different CoCat phases. In marked contrast to previous reports, this reconstruction is not initiated at the surface but at the electrode substrate to catalyst interface. Ex- and in situ investigations of the two borophosphate derived CoCats, as well as the prominent CoPi and CoBi identify differences in the Tafel slope/range, buffer binding and content, long-range order, number of accessible edge sites, redox activity, and morphology. Considering and interconnecting these aspects together with proton mass transport limitations, we provide a comprehensive picture explaining the different OER activities. The most decisive factors are the buffers used for reconstruction, the number of edge sites that are not inhibited by irreversibly bond buffers, and the morphology of the catalysts. With this acquired knowledge, an optimized OER system is realized operating in near neutral potassium borate media at 1.62±0.03 VRHE yielding 250 mA/cm² at 65 °C for one month without degrading performance.

There is an increasing interest to replace precious metal-based catalysts by earth-abundant nonprecious metals due to higher costs, toxicity, and declining availability of the former. Here, the synthesis of a well-defined supported nickel hydrogenation catalyst prepared by surface organometallic chemistry is reported. For this purpose, [LNi(μ-H)]2 (L = HC(CMeNC6H3(iPr)2)2) was grafted on partially dehydroxylated silica to give a homobimetallic H- and O(silica)-bridged Ni2 complex. The structure of the latter was confirmed by infrared spectroscopy, X-ray absorption near-edge structure, and extended X-ray absorption fine structure analyses as well as hydride titration studies. The immobilized catalyst was capable of hydrogenating alkenes and alkynes at low temperatures without prior activation. As an example, ethene can be hydrogenated with an initial turnover frequency of 25.5 min-1 at room temperature.

Transition metal hydroxides (M‐OH) and their heterostructures (X|M‐OH, where X can be a metal, metal oxide, metal chalcogenide, metal phosphide, etc.) have recently emerged as highly active electrocatalysts for hydrogen evolution reaction (HER) of alkaline water electrolysis. Lattice hydroxide anions in metal hydroxides are primarily responsible for observing such an enhanced HER activity in alkali that facilitate water dissociation and assist the first step, the hydrogen adsorption. Unfortunately, their poor electronic conductivity had been an issue of concern that significantly lowered its activity. Interesting advancements were made when heterostructured hydroxide materials with a metallic and or a semiconducting phase were found to overcome this pitfall. However, in the midst of recently evolving metal chalcogenide and phosphide based HER catalysts, significant developments made in the field of metal hydroxides and their heterostructures catalysed alkaline HER and their superiority have unfortunately been given negligible attention. This review, unlike others, begins with the question of why alkaline HER is difficult and will take the reader through evaluation perspectives, trends in metals hydroxides and their heterostructures catalysed HER, an understanding of how alkaline HER works on different interfaces, what must be the research directions of this field in near future, and eventually summarizes why metal hydroxides and their heterostructures are inevitable for energy‐efficient alkaline HER., This review brings out the key advancements made in the field of alkaline HER with metal hydroxides and their heterostructures and also provides a detailed and critical analysis of strategies and perspectives used with highlights on future prospects at the end.

Identifying novel classes of precatalysts for the oxygen evolution reaction (OER by water oxidation) with enhanced catalytic activity and stability is a key strategy to enable chemical energy conversion. The vast chemical space of intermetallic phases offers plenty of opportunities to discover OER electrocatalysts with improved performance. Herein we report intermetallic nickel germanide (NiGe) acting as a superior activity and durable Ni‐based electro(pre)catalyst for OER. It is produced from a molecular bis(germylene)‐Ni precursor. The ultra‐small NiGe nanocrystals deposited on both nickel foam and fluorinated tin oxide (FTO) electrodes showed lower overpotentials and a durability of over three weeks (505 h) in comparison to the state‐of‐the‐art Ni‐, Co‐, Fe‐, and benchmark NiFe‐based electrocatalysts under identical alkaline OER conditions. In contrast to other Ni‐based intermetallic precatalysts under alkaline OER conditions, an unexpected electroconversion of NiGe into γ‐NiIIIOOH with intercalated OH−/CO3 2− transpired that served as a highly active structure as shown by various ex situ methods and quasi in situ Raman spectroscopy., A xanthene‐based bis(germylene)‐Ni complex is used as a molecular precursor for the synthesis of ultra‐small NiGe nanostructures, which can generate a γ‐NiOOH structure with intercalated species. This displays exceptional catalytic activity and long‐term durability for the oxygen evolution reaction (OER).

Herein, we report on intermetallic iron germanide (Fe6Ge5) as a novel oxygen evolution reaction (OER) precatalyst with a Tafel slope of 32 mV dec−1 and an overpotential of 272 mV at 100 mA cm−2 in alkaline media. Furthermore, we uncover the in situ formation of a core–shell like structure that slowly collapses under OER conditions.

Electrocatalytic water splitting is the key process for the formation of green fuels for energy transport and storage in a sustainable energy economy. Besides electricity, it requires water, an aspect that seldomly has been considered until recently. As freshwater is a limited resource (

Based on the low cost and relatively high catalytic activity, considerable efforts have been devoted towards developing redox active transition metal TM oxygen electrocatalysts for the alkaline oxygen evolution reaction OER while the role of redox inactive alkaline earth metals has often been neglected in OER. Herein, for the first time, we developed a novel ternary intermetallic CaFe6Ge6 precatalyst, whose surface rapidly transforms into a porous ultrathin Ca amp; 8722;Fe amp; 8722;O heteroshell structure during alkaline OER through the oxidative leaching of surficial Ge. Benefiting from synergistic effects, this highly efficient OER active material with distinct Ca amp; 8722;Fe amp; 8722;O layers has a large electrochemical surface area and more exposed active Fe sites than a Ca free FeOx phase. Also, the presence of Ca in Ca amp; 8722;Fe amp; 8722;O is responsible for the enhanced transport and activation of hydroxyls and related OER reaction intermediate as unequivocally illustrated by a combination of quasi in situ Raman spectroscopy and various ex situ methods

The electrochemical oxygen reduction reaction ORR offers a most promising and efficient route to produce hydrogen peroxide H2O2 , yet the lack of cost effective and high performance electrocatalysts have restricted its practical application. Herein, an entropy enhancement strategy has been employed to enable the low cost perovskite oxide to effectively catalyze the electrosynthesis of H2O2. The optimized Pb NiWMnNbZrTi 1 6O3 ceramic is available on a kilogram scale and displays commendable ORR activity in alkaline media with high selectivity over 91 amp; 8201; across the wide potential range for H2O2 including an outstanding degradation property for organic dyes through the Fenton process. The exceptional performance of this perovskite oxide is attributed to the entropy stabilization induced polymorphic transformation assuring the robust structural stability, decreased charge mobility as well as synergistic catalytic effects which we confirm using advanced in situ Raman, transient photovoltage, Rietveld refinement as well as finite elemental analysis

Transition metals, in particular noble metals, are the most common species in metal-mediated water electrolysis because they serve as highly active catalytic sites. In many cases, the presence of nontransition metals, that is, s-, p-, and f-block metals with high natural abundance in the earth-crust in the catalytic material is indispensable to boost efficiency and durability in water electrolysis. This is why alkali metals, alkaline-earth metals, rare-earth metals, lean metals, and metalloids receive growing interest in this research area. In spite of the pivotal role of these nontransition metals in tuning efficiency of water electrolysis, there is far more room for developments toward a knowledge-based catalyst design. In this review, five classes of nontransition metals species which are successfully utilized in water electrolysis, with special emphasis on electronic structure-catalytic activity relationships and phase stability, are discussed. Moreover, specific fundamental aspects on electrocatalysts for water electrolysis as well as a perspective on this research field are also addressed in this account. It is anticipated that this review can trigger a broader interest in using s-, p-, and f-block metals species toward the discovery of advanced polymetal-containing electrocatalysts for practical water splitting.

The carbon dioxide reduction reaction (CO2RR), in particular electrochemically, to produce carbonaceous fuels is considered as a viable approach to store energy and to enable a CO2-neutral carbon m...

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu9S5 has been prepared from a molecular copper(I) precursor, [{(PyHS)2CuI(PyHS)}2](OTf)2 (1), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu9S5, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu9S5/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm−2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO2 and IrO2 electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu9S5/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu9S5 can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu9S5 that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals., Copper as the topper. The Digenite mineral Cu9S5 phase has been produced from a molecular CuI 2S2 precursor complex and applied for efficient electrocatalytic alkaline oxygen evolution reaction, displaying competent catalytic activity and stability.

Herein, we demonstrate a template directed route for the synthesis of self-supported cobalt-iron based Prussian blue analogues (PBAs). The PBAs are electrochemically transformed into layered double hydroxides to produce excellent water oxidation and hydrogen evolution activity, while the overall water splitting is attained at a cell voltage of 1.58 V to reach 20 mA cm-2 current density.

The oxygen evolution reaction (OER) and the value-added selective oxidation of renewable organic substrates are the most promising reactions to supply electrons and protons for the synthesis of sustainable fuels. To meet industrial requirements, new methods for a simple, fast, environmentally friendly, and cheap synthesis of robust, self-supported, high surface area electrodes are required. Herein, we report on a novel in liquid plasma electrolysis approach for the growth of hierarchical nanostructures on nickel foam. Under retention of the morphology, iron could be incorporated into this high surface area electrode. For the oxidation of 5-hydroxymethylfurfural and benzyl alcohol, the iron free plasma treated electrode is more suitable reaching current densities up to 800 mA/cm² with Faradaic efficiencies above 95%. For the OER, the iron incorporated nickel foam electrode reached the industrially relevant current density of 500 mA/cm² at 1.473±0.013 VRHE (60 °C) and showed no activity decrease over 140 h. The different effects of the iron doping is rationalised using MeOH doping and in situ Raman spectroscopy. Furthermore, we could separate changes in intrinsic activity per active site and number of active sites for the OER as well as reveal diffusion limitations of the organic oxidation reactions which we explain with respect to the surface morphology. We anticipate that the plasma modified high surface area nickel foam could potentially be applied for various electrocatalytic processes.

As the kinetically demanding oxygen evolution reaction (OER) is crucial for the decarbonization of our society, a wide range of (pre)catalysts with various non-active-site elements (e.g., Mo, S, Se, N, P, C, Si…) have been investigated. Thermodynamics dictate that these elements oxidize during industrial operation. The formed oxyanions are water soluble and thus predominantly leach in a reconstruction process. Nevertheless, recently, it was unveiled that these thermodynamically stable (oxy)anions can adsorb on the surface or intercalate in the interlayer space of the active catalyst. There, they tune the electronic properties of the active sites and can interact with the reaction intermediates, changing the OER kinetics and potentially breaking the persisting OER *OH/*OOH scaling relations. Thus, the addition of (oxy)anions to the electrolyte opens a new design dimension for OER catalysis and the herein discussed observations deepen the understanding of the role of anions in the OER.

Following the example of photovoltaics, one approach to large-scale photocatalytic hydrogen production is the irradiation of a correspondingly large catalyst area. Paper production is a process in which large areas can already be produced based on the main component: cellulose. Herein, the TiO2 photocatalyst modification PC500, which also uses platinum nanoparticles as a cocatalyst, is supported in two different ways using cellulose. On the one hand, the catalyst is fixed to the surface of a commercial filter paper and, on the other hand, a photocatalytic paper is produced. For comparison, the catalyst is immobilized by means of drop coating using Nafion and measured as a suspension. The cellulose-stabilized films are active and hydrogen production is comparable with the activity obtained from the drop-coating method. The experiments show that the aggregation behavior of cellulose can be used to produce photocatalytically active films. The preparation is easy and can be applied to different kinds of (photo)catalysts. Although the films are very active, their stability during reaction due to swelling and hydrogen production must be further improved.

Developing advanced electrocatalysts with exceptional two electron 2e amp; 8722; selectivity, activity, and stability is crucial for driving the oxygen reduction reaction ORR to produce hydrogen peroxide H2O2 . Herein, a composition engineering strategy is proposed to flexibly regulate the intrinsic activity of amorphous nickel boride nanoarchitectures for efficient 2e amp; 8722; ORR by oriented reduction of Ni2 with different amounts of BH4 amp; 8722;. Among borides, the amorphous NiB2 delivers the 2e amp; 8722; selectivity close to 99 at 0.4 V and over 93 in a wide potential range, together with a negligible activity decay under prolonged time. Notably, an ultrahigh H2O2 production rate of 4.753 mol gcat amp; 8722;1 h amp; 8722;1 is achieved upon assembling NiB2 in the practical gas diffusion electrode. The combination of X ray absorption and in situ Raman spectroscopy, as well as transient photovoltage measurements with density functional theory, unequivocally reveal that the atomic ratio between Ni and B induces the local electronic structure diversity, allowing optimization of the adsorption energy of Ni toward OOH and reducing of the interfacial charge transfer kinetics to preserve the O amp; 63743;O bond

A robust and efficient route to modify the chemical and physical properties of polycrystalline copper (Cu) wires via versatile plasma electrolysis is presented. Silica (SiO$_{2}$) nanoparticles (11 nm) are introduced during the electrolysis to tailor the surface structure of the Cu electrode. The influence of these SiO$_{2}$ nanoparticles on the structure of the Cu electrodes during plasma electrolysis over a wide array of applied voltages and processing time is investigated systematically. Homogeneously distributed 3D coral-like microstructures are observed by scanning electron microscopy on the Cu surface after the in-liquid plasma treatment. These 3D microstructures grow with increasing plasma processing time. Interestingly, the microstructured copper electrode is composed of CuO as a thin outer layer and a significant amount of inner Cu$_{2}$O. Furthermore, the oxide film thickness (between 1 and 70 µm), the surface morphology, and the chemical composition can be tuned by controlling the plasma parameters. Remarkably, the fabricated microstructures can be transformed to nanospheres assembled in coral-like microstructures by a simple electrochemical treatment.

Vacancy engineering is deemed as one of the powerful protocols to tune the catalytic activity of electrocatalysts. Herein, Se vacancy with charge polarization is created in the NiSe2 structure NiSe2 VSe via a sequential phase conversion strategy. By a combined analysis of the Rietveld method, transient photovoltage spectra TPV , in situ Raman and density functional theory DFT calculation, it is unequivocally discovered that the presence of charge polarized Se vacancy is beneficial for stabilizing the structure, decreasing the electron transfer kinetics, as well as optimizing the free adsorption energy of reaction intermediate during two electron oxygen reduction reaction 2e amp; 8722; ORR . Benefiting from these merits, the as prepared NiSe2 VSe delivered the highest selectivity of 96 toward H2O2 in alkaline media, together with a selectivity higher than 90 over the wide potential range from 0.25 to 0.55 V, ranking it in the top level among the previously reported transition metal based electrocatalysts. Most notably, it also displayed admirable stability with only a slight selectivity decay after 5000 cycles of accelerated degradation test ADT

The continuous increase in the population and industrial development has led to an increase in global energy demand. Most of the current primary energy consumption is obtained from the burning of fossil fuels that releases an enormous amount of greenhouse gases. Notably, hydrogen (H2) is a clean and eco-friendly fuel and has already shown its ability to be a promising substitute for fossil energy. One of the cleanest ways to produce H2 is by splitting of water by electrolysis.1 Recently, numerous inexpensive and robust catalysts based on transition metals (oxides, chalcogenides, pnictides, carbides, or alloys, etc.) have been developed for water splitting with reasonable activity.2 Despite the massive development of electrocatalysts for water splitting, huge challenges still exist for their use in practical application. Our current goals are to uncover new classes of suitable unconventional catalysts based on non-noble metals that can offer better overall catalytic efficiency for practical applications; to study their structural transformation, active sites, surface, and bulk structures; and to investigate the influence of precatalysts on the properties of the final catalyst. In this context, intermetallic compounds have numerous advantages owing to their intriguing structural, chemical and physical properties, especially being catalytically active and electrically conductive at the same time and thus, making them an ideal class of materials for electrocatalytic applications.3 Using different approaches, we synthesized various classes of intermetallic materials (e.g., stannides, gallides, germanides, indates, silicides, etc.) with interesting structural and electronic features.4-5 Most of these materials exhibited remarkable electrocatalytic activity for water splitting, yielding considerably low overpotentials with enhanced long-term durability for both O2 and H2 generation in alkaline media. The active catalyst structure during each half-reaction (H2 and O2) and the correlation of the structure with the activity of the catalysts were revealed by a profound understanding of the system using in-situ and ex-situ techniques. This talk will provide a brief summary of the ongoing water splitting research as well as delve into selected examples of our recent work to pave the way to a concept-guided design system beyond water electrolysis (e.g., paired electrolysis). References [1] H Yang, M Driess, P. W. Menezes, Adv. Energy Mater. 2021, 11, 2102074. [2] Z Chen, H Yang, Z Kang, M Driess, P. W. Menezes, Adv. Mater. 2022, 2108432. [3] C. Walter, P. W. Menezes, M. Driess, Chem. Sci. 2021, 12, 8603. [4] N. Hausmann, R. Beltrán-Suito, S. Mebs, V. Hlukhyy, T. F. Fässler, H. Dau, M. Driess, P. W. Menezes, Adv. Mater. 2021, 33, 2008823. [5] B. Chakraborty, R. Beltrán-Suito, S. Garai, J. N. Hausmann, M. Driess, P. W. Menezes, Adv. Energy Mater. 2020, 10, 2001377.

The oxygen evolution reaction (OER) is the most likely reaction to supply electrons and protons for future green fuel and chemical formation, and thus many materials have been studied for their suitability as OER (pre)catalysts. However, in-situ and post-catalytic studies have shown that the harsh OER conditions alter the electrode materials, causing a reconstruction to mainly transition metal oxyhydroxides in alkaline and near-neutral electrolyte. As this reconstructed phase is the real catalyst, its atomic structure and physical properties must be precisely known. These properties will be affected by the precatalyst and the reconstruction conditions, like the product of a chemical reaction is affected by the substrate and reaction conditions. For the elucidation of such reconstruction processes, a broad range of spectroscopic (in-situ) methods combined with new, meaningful precursors are required. Herein, investigations on the reconstruction of several precatalysts such as phosphites,1 borophosphates,2 selenites,3 silicides,4 and elemental metal foams are presented. These reconstructions were analysed by in situ Raman and X-ray absorption spectroscopy together with state-of-the-art post-mortem characterization techniques. In an effort to connect this data, we propose ideas relating the precatalyst structure with the one of the formed oxyhydroxides. Additionally, we critically debate the question: why should a non-oxyhydroxide phase be used for the OER if it will anyway reconstruct? Moreover, as mentioned, also the reconstruction conditions affect the specific nature of the formed oxyhydroxide. Considering this, we present a case, where from the same precatalyst, catalysts with entirely different structural and electrocatalytic properties were obtained by only changing the electrochemical reconstruction conditions (potential, pH, electrolyte composition...). References: Menezes, P. W. et al. A structurally versatile nickel phosphite acting as a robust bifunctional electrocatalyst for overall water splitting. Energy Environ. Sci. 11, 0–13 (2018). Menezes, P. W. et al. Helical cobalt borophosphates to master durable overall water-splitting. Energy Environ. Sci. 12, 988–999 (2019). Hausmann, J. N. et al. Understanding the formation of bulk- and surface-active layered (oxy)hydroxides for water oxidation starting from a cobalt selenite precursor. Energy Environ. Sci. 13, 3607–3619 (2020). Hausmann, J. N. et al. Evolving Highly Active Oxidic Iron(III) Phase from Corrosion of Intermetallic Iron Silicide to Master Efficient Electrocatalytic Water Oxidation and Selective Oxygenation of 5‐Hydroxymethylfurfural. Adv. Mater. 33, 2008823 (2021). Figure 1

A facile synthetic route to NiPt3@NiS heteronanostructures is reported, starting from a subsulfido bridged heterobimetallic nickel-platinum molecular precursor. Notably, the NiPt3@NiS on nickel foam displayed merely an overpotential of 12 mV at -10 mA cm-2, which is substantially lower than that of Pt or NiS, synthesized through a similar approach and represents the most active hydrogen evolution reaction (HER) electrocatalysts yet reported in alkaline solutions. NiPt3@NiS electrodes demonstrated an unceasing HER stability over 8 days, which is well over those reported for Pt-based catalysts signifying a capability of scaled hydrogen production.

Electrochemical splitting of water to oxygen and hydrogen using earth-abundant first-row transition metal-based catalysts is a promising approach for sustainable energy conversion. Herein, we prese...

In a green energy economy, electrocatalysis is essential for chemical energy conversion and to produce value added chemicals from regenerative resources. To be widely applicable, an electrocatalyst should comprise the Earth's crust's most abundant elements. The most abundant 3d metal, iron, with its multiple accessible redox states has been manifold applied in chemocatalytic processes. However, due to the low conductivity of FeIII Ox Hy phases, its applicability for targeted electrocatalytic oxidation reactions such as water oxidation is still limited. Herein, it is shown that iron incorporated in conductive intermetallic iron silicide (FeSi) can be employed to meet this challenge. In contrast to silicon-poor iron-silicon alloys, intermetallic FeSi possesses an ordered structure with a peculiar bonding situation including covalent and ionic contributions together with conducting electrons. Using in situ X-ray absorption and Raman spectroscopy, it could be demonstrated that, under the applied corrosive alkaline conditions, the FeSi partly forms a unique, oxidic iron(III) phase consisting of edge and corner sharing [FeO6 ] octahedra together with oxidized silicon species. This phase is capable of driving the oxyge evolution reaction (OER) at high efficiency under ambient and industrially relevant conditions (500 mA cm-2 at 1.50 ± 0.025 VRHE and 65 °C) and to selectively oxygenate 5-hydroxymethylfurfural (HMF).

Intermetallic compounds exhibit attractive electronic, physical, and chemical properties, especially in terms of a high density of active sites and enhanced conductivity, making them an ideal class of materials for electrocatalytic applications. Nevertheless, widespread use of intermetallics for such applications is often limited by the complex energy-intensive processes yielding larger particles with decreased surface areas. In this regard, alternative synthetic strategies are now being explored to realize intermetallics with distinct crystal structures, morphology, and chemical composition to achieve high performance and as robust electrode materials. In this perspective, we focus on the recent advances and progress of intermetallics for the reaction of electrochemical water-splitting. We first introduce fundamental principles and the evaluation parameters of water-splitting. Then, we emphasize the various synthetic methodologies adapted for intermetallics and subsequently, discuss their catalytic activities for water-splitting. In particular, importance has been paid to the chemical stability and the structural transformation of the intermetallics as well as their active structure determination under operating water-splitting conditions. Finally, we describe the challenges and future opportunities to develop novel high-performance and stable intermetallic compounds that can hold the key to more green and sustainable economy and rise beyond the horizon of water-splitting application., This perspective provides an overview of the versatility of intermetallic compounds for electrochemical water splitting along with their synthetic strategies, catalytic efficiencies as well as their active structures under operating conditions.

Herein, we report on intermetallic iron germanide (Fe6Ge5) as a novel oxygen evolution reaction (OER) precatalyst with a Tafel slope of 32 mV dec-1 and an overpotential of 272 mV at 100 mA cm-2 in alkaline media. Furthermore, we uncover the in situ formation of a core-shell like structure that slowly collapses under OER conditions.

Plasma electrolysis is proposed for surface engineering of copper electrodes. Silica nanoparticles are crucial for fabricating 3D coral‐like microstructures, whose growth and the resulting EASA can be actively fine‐tuned. The plasma‐treated copper surfaces are composed of a thin outer shell of copper(II) oxide and a core of copper(I) oxide. Electrochemical treatment enables the structural transformation from microstructures to nanosphere assemblies. A robust and efficient route to modify the chemical and physical properties of polycrystalline copper (Cu) wires via versatile plasma electrolysis is presented. Silica (SiO2) nanoparticles (11 nm) are introduced during the electrolysis to tailor the surface structure of the Cu electrode. The influence of these SiO2 nanoparticles on the structure of the Cu electrodes during plasma electrolysis over a wide array of applied voltages and processing time is investigated systematically. Homogeneously distributed 3D coral‐like microstructures are observed by scanning electron microscopy on the Cu surface after the in‐liquid plasma treatment. These 3D microstructures grow with increasing plasma processing time. Interestingly, the microstructured copper electrode is composed of CuO as a thin outer layer and a significant amount of inner Cu2O. Furthermore, the oxide film thickness (between 1 and 70 µm), the surface morphology, and the chemical composition can be tuned by controlling the plasma parameters. Remarkably, the fabricated microstructures can be transformed to nanospheres assembled in coral‐like microstructures by a simple electrochemical treatment., publishedVersion