Search

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.

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.

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).

Visible light‐driven photocatalytic reduction of protons to H2 is considered a promising way of solar‐to‐chemical energy conversion. Effective transfer of the photogenerated electrons and holes to the surface of the photocatalyst by minimizing their recombination is essential for achieving a high photocatalytic activity. In general, a sacrificial electron donor is used as a hole scavenger to remove photogenerated holes from the valence band for the continuation of the photocatalytic hydrogen (H2) evolution process. Here, for the first time, the hole‐transfer dynamics from Pt‐loaded sol−gel‐prepared graphitic carbon nitride (Pt‐sg‐CN) photocatalyst were investigated using different adsorbed hole acceptors along with a sacrificial agent (ascorbic acid). A significant increment (4.84 times) in H2 production was achieved by employing phenothiazine (PTZ) as the hole acceptor with continuous H2 production for 3 days. A detailed charge‐transfer dynamic of the photocatalytic process in the presence of the hole acceptors was examined by time‐resolved photoluminescence and in situ electron paramagnetic resonance studies., Holes to achieve goals: Efficient separation and transfer of holes from the graphitic carbon nitride to enhance the photocatalytic hydrogen evolution is achieved using hole‐transfer agents. A significant increment (4.84 times) in H2 production is achieved by employing phenothiazine as the hole acceptor with continuous H2 production for 3 days.

The urgent need for a stable, efficient, and affordable oxygen evolution reaction (OER) catalyst has led to the investigation of a vast amount of transition metal materials with multiple different anions. In situ and post catalytic characterization shows that most materials transform during the harsh OER conditions to layered (oxy)hydroxides (LOH). Several open questions concerning these in situ formed LOH remain such as: an explanation for their strongly varying activities, or the effect of the precatalyst structure, leaching anions, and transformation conditions on the formed LOH. Herein, we report on a cobalt selenite precursor, which, depending on pH and potential, transforms irreversibly into two different LOH OER catalysts. Combining multiple electrochemical and analytical methods ex and in situ, we prove that one of these products is near-surface catalytically active and the other one throughout the bulk with an in situ average cobalt oxidation state of 3.2. We deduce a detailed structural model explaining these differences and propose general concepts relating both the precatalyst structure and the transformation conditions to the final catalyst. Further, we apply these models to the most promising non-noble metal catalyst, NiFe LOH.

Electrochemical water splitting remains a frontier research topic in the quest to develop artificial photosynthetic systems by using noble metal‐free and sustainable catalysts. Herein, a highly crystalline CuSe has been employed as active electrodes for overall water splitting (OWS) in alkaline media. The pure‐phase klockmannite CuSe deposited on highly conducting nickel foam (NF) electrodes by electrophoretic deposition (EPD) displayed an overpotential of merely 297 mV for the reaction of oxygen evolution (OER) at a current density of 10 mA cm−2 whereas an overpotential of 162 mV was attained for the hydrogen evolution reaction (HER) at the same current density, superseding the Cu‐based as well as the state‐of‐the‐art RuO2 and IrO2 catalysts. The bifunctional behavior of the catalyst has successfully been utilized to fabricate an overall water‐splitting device, which exhibits a low cell voltage (1.68 V) with long‐term stability. Post‐catalytic analyses of the catalyst by ex‐situ microscopic, spectroscopic, and analytical methods confirm that under both OER and HER conditions, the crystalline and conductive CuSe behaves as an electro(pre)catalyst forming a highly reactive in situ crystalline Cu(OH)2 overlayer (electro(post)catalyst), which facilitates oxygen (O2) evolution, and an amorphous Cu(OH)2/CuOx active surface for hydrogen (H2) evolution. The present study demonstrates a distinct approach to produce highly active copper‐based catalysts starting from copper chalcogenides and could be used as a basis to enhance the performance in durable bifunctional overall water splitting., Transform to perform: A highly crystalline klockmannite CuSe has been used as an efficient bifunctional electro(pre)catalyst for the reaction of alkaline water splitting and, subsequently, its active structure at the anode and cathode has been uncovered.

With the rapid development of wearable electronic devices, multifunctional ultrarobust, thermoconductive, nonflammable, and electromagnetic interference (EMI) shielding films which are widely utilized to efficiently dissipate heat generated from electronic components are in high demand. The poor scalability and mechanical flexibility of multifunctional papers usually hinder their practical application. In this study, mass-scalable ultrarobust graphene nanoplatelet (GnP) cross-linked aramid nanofiber (ANF) papers with a nacre-bioinspired structure are fabricated via an evaporation-induced self-assembly approach. By chemical cross-linking between two-dimensional GnPs and one-dimensional ANFs in the nacre-bioinspired structure by a phosphorus agent, the excellent toughness and folding endurance of the GnP based ANF papers have been successfully achieved with simultaneous integration of high-level multifunctional properties. Specifically, the ultrarobust GnP based ANF paper with 50 wt% GnP loading exhibits exceptional ultimate tensile strength (437 MPa), Young's modulus (19.7 GPa) and toughness (23.9 MJ m−3) as well as superb folding endurance after 10 000 bending cycles. Moreover, the highly ordered alignment of GnP induced an unprecedented thermal/electrical conductivity, and the GnP (50 wt%) based ANF papers with an ultrathin thickness of 21 μm show a superb in-plane thermal conductivity (up to 68.2 W m−1 K−1) and outstanding absolute effectiveness EMI shielding (up to 11 060 dB cm2 g−1) and are comparable with some commercial metals/alloys. These outstanding mechanical flexibility integrated superb thermal/EMI properties along with mass-scale production pave the way for practical applications of GnP based ANF papers in the development of advanced thermal management materials in autonomous cars, air vehicles and wearable devices.

The single source precursor (SSP) approach was used to prepare highly active CoP bifunctional electro(pre)catalysts for the oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and overall water splitting (OWS) reaction starting from a molecular β-diketiminato Co(I) cyclo-P4 complex. Crystalline or amorphous CoP particles were attained depending on the preparation route. Notably, the amorphous CoP displayed higher activity compared to the crystalline CoP on nickel foam (NF) and fluorinated tin oxide (FTO) substrates due to its unique electronic properties and surface characteristics. During the OER, severe oxidation to Co-oxy(hydroxides)/oxides by the loss of P was found to be crucial to increase the concentration of CoOx active sites. Interestingly, complete leaching of surface P from CoP and surface Co enrichment occurred during the HER. Finally, an OWS device was fabricated where the amorphous CoP outperformed the crystalline CoP with respect to low OWS cell voltage (with a difference of 130 mV) and enhanced stability for 5 days.