Structural and Electronic Factors behind the Electrochemical Stability of 3D-Metal Tungstates under Oxygen Evolution Reaction Conditions.

Transition metal tungstates (TMTs) possess a wolframite-like lattice structure and preferably form via an electrostatic interaction between a divalent transition metal cation (MII) and an oxyanion of tungsten ([WO4]2-). A unit cell of a TMT is primarily composed of two repeating units, [MO6]oh and [WO6]oh, which are held together via several M-µ2-O-W bridging links. The bond character (ionic or covalent) of this bridging unit determines the stability of the lattice and influences the electronic structure of the bulk TMT materials. Recently, TMTs have been successfully employed as an electrode material for various applications, including electrochemical water splitting. Despite the wide electrocatalytic applications of TMTs, the study of the structure-activity correlation and electronic factors responsible for in situ structural evolution to electroactive species during electrochemical reactions is still in its infancy. Herein, a series of TMTs, MIIWVIO4 (M = Mn/Fe/Co/Ni), have been prepared and employed as electrocatalysts to study the oxygen evolution reaction (OER) under alkaline conditions and to scrutinize the role of transition metals in controlling the energetics of the formation of electroactive species. Since the [WO6]oh unit is common in the TMTs considered, the variation of the central atom of the corresponding [MO6]oh unit plays an intriguing role in controlling the electronic structure and stability of the lattice under anodic potential. Under the OER conditions, a potential-dependent structural transformation of MWO4 is noticed, where MnWO4 appears to be the most labile, whereas NiWO4 is stable up to a high anodic potential of ∼1.68 V (vs RHE). Potential-dependent hydrolytic [WO4]2- dissolution to form MOx active species, traced by in situ Raman and various spectro-/microscopic analyses, can directly be related to the electronic factors of the lattice, viz., crystal field splitting energy (CFSE) of MII in [MO6]oh, formation enthalpy (ΔHf), decomposition enthalpy (ΔHd), and Madelung factor associated with the MWO4 ionic lattice. Additionally, the magnitude of the Löwdin and Bader charges on M of the M-µ2-O-W bond is directly related to the degree of ionicity or covalency in the MWO4 lattice, which indirectly influences the electronic structure and activity. The experimental results substantiated by the computational study explain the electrochemical activity of the TMTs with the help of various structural and electronic factors and bonding interactions in the lattice, which has never been realized. Therefore, the study presented here can be taken as a general guideline to correlate the reactivity to the structure of the inorganic materials.

Elevated temperature-driven coordinative reconstruction of an unsaturated single-Ni-atom structure with low valency on a polymer-derived matrix for the electrolytic oxygen evolution reaction.

A high-temperature pyrolysis-controlled coordination reconstruction resulted in a single-Ni-atom structure with a Ni-Nx-C structural unit (x = N atom coordinated to Ni). Pyrolysis of Ni-phen@ZIF-8-RF at 700 °C resulted in NiNP-NC-700 with predominantly Ni nanoparticles. Upon elevating the pyrolysis temperature from 700 to 900 °C, a coordination reconstruction offers Ni-Nx atomic sites in NiSA-NC-900. A combined investigation with X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and soft X-ray L3-edge spectroscopy suggests the stabilization of low-valent Niδ+ (0 < δ < 2) in the Ni-N-C structural units. The oxygen evolution reaction (OER) is a key process during water splitting in fuel cells. However, OER is a thermodynamically uphill reaction with multi-step proton-coupled electron transfer and sluggish kinetics, due to which there is a need for a catalyst that can lower the OER overpotentials. The adsorption energy of a multi-step reaction on a single metal atom with coordination unsaturation tunes the adsorption of each oxygenated intermediate. The promising OER activity of the NiSA-NC-900/NF anode on nickel foam was followed by the overall water splitting (OWS) using using NiSA-NC-900/NF as anode and Pt coil as the cathodic counterpart, wherein a cell potential of 1.75 V at 10 mA cm-2 was achieved. The cell potential recorded with Pt(-)/(+)NiSA-NC-900/NF was much lower than that obtained for other cells, i.e., Pt(-)/NF and NF(-)/(+)NF, which enhances the potentials of low-valent NiSAs for insightful understanding of the OER. At a constant applied potential of 1.61 V (vs. RHE) for 12 h, an small increase in current for initial 0.6 h followed by a constant current depicts the fair stability of catalyst for 12 h. Our results offer an insightful angle into the OER with a coordinatively reconstructed single-Ni-atom structure at lower valency (<+2).

Redox-active Sn(II) to lead to SnFe2O4 spinel as a bi-functional water splitting catalyst.

Despite several reports on metal ferrites for water splitting studies, SnFe2O4 is a rarely explored spinel oxide. Herein, solvothermally prepared ca. 5 nm SnFe2O4 nanoparticles deposited on nickel foam (NF) behaves as a bi-functional electrocatalyst. In alkaline pH, the SnFe2O4/NF electrode exhibits oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) at moderate overpotentials and shows a fair chronoamperometric stability. Detailed study indicates that iron sites of the spinel are preferably active for the OER while the SnII sites not only enhance the electrical conductivity of the material but also favor the HER.

Integrating Electrochemical CO2 Reduction on α-NiS with the Water or Organic Oxidations by Its Electro-Oxidized NiO(OH) Counterpart to an Artificial Photosynthetic Scheme.

Efficient hydrogen production, biomass up-conversion, and CO2-to-fuel generation are the key challenges of the present decade. Electrocatalysis in aqueous electrolytes by choosing suitable transition-metal-based electrode materials remains the green approach for the trio of sustainable developments. Given that, finding electrode materials with multifunctional capability would be beneficial. Herein, the nanocrystalline α-NiS, synthesized solvothermally, has been chosen as an electrode material. As the first step to construct an electrolyzer, α-NiS deposited on conducting nickel foam (NF) has been used as an anode, and under the anodic potential, the α-NiS particles have lost sulfides to the electrolyte and transform to amorphous electro-derived NiO(OH) (NiO(OH)ED), confirmed by different spectroscopic and microscopic studies. In situ transformation of α-NiS to amorphous NiO(OH)ED results in an enhancement of the electrochemical surface area and not only becomes active toward oxygen evolution reaction (OER) at a moderate overpotential of 264 mV (at 20 mA cm-2) but also can convert a series of biomass-derived organic compounds, namely, 2-hydroxymethylfurfural (HMF), 2-furfural (FF), ethylene glycol (EG), and glycerol (Gly), to industrially relevant feedstocks with a high (∼96%) Faradaic efficiency. During these organic oxidations, NiO(OH)ED/NF participate in the multiple-electron oxidation process (up to 8e-) including C-C bond cleavages of EG and Gly. During the cathodic performance of the α-NiS/NF, the structural integrity has been retained and the unaltered α-NiS/NF electrode remains more effective cathode for alkaline hydrogen evolution reaction (HER) and CO2 reduction (CO2R) compared to its in situ-derived NiO(OH)ED/NF. α-NiS/NF can reduce the CO2 predominantly to CO even at a higher potential like -0.8 V (vs RHE). The fabricated cell with α-NiS and its electro-oxidized NiO(OH)ED counterpart, α-NiS/NF(-)/(+)NiO(OH)ED/NF, is able to show an artificial photosynthetic scheme in which the NiO(OH)ED/NF anode oxidizes water to O2 and the α-NiS cathode reduces CO2 majorly to CO in a moderate cell potential. In this study, α-NiS has been utilized as a single electrode material to perform multiple sustainable transformations.

γ-FeO(OH) with multiple surface terminations: Intrinsically active for the electrocatalytic oxygen evolution reaction.

Due to poor conductivity, the electrocatalytic performance of independently prepared iron oxy-hydroxide (FeO(OH)) is inferior whereas FeO(OH) derived in situ from the iron based electro(pre)catalyst shows superior performance in the oxygen evolution reaction (OER). Use of mixed phase FeO(OH) and/or incorporation of CoII/NiII metal into the FeO(OH) structure has also been demonstrated as a convenient approach to achieve high OER activity. Nevertheless, preparation of phase-pure, albeit active FeO(OH) material with fair electrochemical performance remains a perdurable challenge. Moreover, the role of the crystalline phase and its surface structure in controlling the OER activity is still unclear. Herein, a simple synthetic protocol has been developed to prepare a series of phase-pure α-FeO(OH) (goethite) and γ-FeO(OH) (lepidocrocite) materials. By changing the reaction conditions such as iron salt and reaction temperature, the crystallinity as well as the phase of the oxy-hydroxide material have been varied. The isolated α- and γ-FeO(OH) materials with different crystallinity were thereafter deposited on nickel foam (NF) for alkaline OER study. The recorded overpotential value at 10 mA cm-2 has been found to be dependent on the phase and crystallinity of the FeO(OH) materials. The partially crystalline γ-FeO(OH) isolated at room temperature (γ-FeO(OH)@RT) turns out to be the most active with a lowest overpotential of 260 mV at 10 mA cm-2 and a long term stability of 12 h. The γ-FeO(OH)@RT/NF anode can furnish high current densities like 50-100 mA cm-2 which makes this anode distinct from the previously reported FeO(OH) materials. Detailed electrochemical study suggested that the fair activity of the γ-FeO(OH)@RT arises due to a facile electrokinetics as evident from the small Tafel slope and charge transfer resistance (Rct value from the Nyquist plot). Owing to the superior activity of the γ-FeO(OH)@RT/NF, the anode can further be incorporated into an overall water splitting electrolyzer that can operate at a cell potential of 1.68 V. The microscopic characterization provides concrete evidence in support of the polycrystallinity of the γ-FeO(OH)@RT. The superior activity of the γ-FeO(OH)@RT perhaps can be correlated to its polycrystalline nature with more defect edges, the presence of a large exposed surface and random atomic arrangements. The highest degree of multiple surface active terminals (-O, -OH and -Fe) available in this polycrystalline γ-FeO(OH) perhaps makes the catalyst more active compared to the crystalline FeO(OH) analogue with a limited number of surface terminals. From a comparative study with a series of FeO(OH) materials, this work highlights a direct relationship between the surface functionality and the electrochemical activity of the FeO(OH) material.

Intrinsic Lability of NiMoO4 to Excel the Oxygen Evolution Reaction.

Nickel-based bimetallic oxides such as NiMoO4 and NiWO4, when deposited on the electrode substrate, show remarkable activity toward the electrocatalytic oxygen evolution reaction (OER). The stability of such nanostructures is nevertheless speculative, and catalytically active species have been less explored. Herein, NiMoO4 nanorods and NiWO4 nanoparticles are prepared via a solvothermal route and deposited on nickel foam (NF) (NiMoO4/NF and NiWO4/NF). After ensuring the chemical and structural integrity of the catalysts on electrodes, an OER study has been performed in the alkaline medium. After a few cyclic voltammetry (CV) cycles within the potential window of 1.0-1.9 V (vs reversible hydrogen electrode (RHE)), ex situ Raman analysis of the electrodes infers the formation of NiO(OH)ED (ED: electrochemically derived) from NiMoO4 precatalyst, while NiWO4 remains stable. A controlled study, stirring of NiMoO4/NF in 1 M KOH without applied potential, confirms that NiMoO4 hydrolyzes to the isolable NiO, which under a potential bias converts into NiO(OH)ED. Perhaps the more ionic character of the Ni-O-Mo bond in the NiMoO4 compared to the Ni-O-W bond in NiWO4 causes the transformation of NiMoO4 into NiO(OH)ED. A comparison of the OER performance of electrochemically derived NiO(OH)ED, NiWO4, ex-situ-prepared Ni(OH)2, and NiO(OH) confirmed that in-situ-prepared NiO(OH)ED remained superior with a substantial potential of 238 (±6) mV at 20 mA cm-2. The notable electrochemical performance of NiO(OH)ED can be attributed to its low Tafel slope value (26 mV dec-1), high double-layer capacitance (Cdl, 1.21 mF cm-2), and a low charge-transfer resistance (Rct, 1.76 Ω). The NiO(OH)ED/NF can further be fabricated as a durable OER anode to deliver a high current density of 25-100 mA cm-2. Post-characterization of the anode proves the structural integrity of NiO(OH)ED even after 12 h of chronoamperometry at 1.595 V (vs reversible hydrogen electrode (RHE)). The NiO(OH)ED/NF can be a compatible anode to construct an overall water splitting (OWS) electrolyzer that can operate at a cell potential of 1.64 V to reach a current density of 10 mA cm-2. Similar to that on NF, NiMoO4 deposited on iron foam (IF) and carbon cloth (CC) also electrochemically converts into NiO(OH) to perform a similar OER activity. This work understandably demonstrates monoclinic NiMoO4 to be an inherently unstable electro(pre)catalyst, and its structural evolution to polycrystalline NiO(OH)ED succeeding the NiO phase is intrinsic to its superior activity.