Post-synthetic Metalation on the Ionic TiO2 Surface to Enhance Metal-CO2 Interaction During Photochemical CO2 Reduction.

During the photochemical CO2 reduction reaction, CO2 adsorption on the catalyst's surface is a crucial step where the binding mode of the [metal-CO2] adduct directs the product selectivity and efficiency. Herein, an ionic TiO2 nanostructure stabilized by polyoxometalates (POM), ([POM]x@TiO2), is prepared and the sodium counter ions present on the surface to balance the POMs' charge are replaced with copper(II) ions, (Cux[POM]@TiO2). The microscopic and spectroscopic studies affirm the copper exchange without altering the TiO2 core and weak coordination of copper (II) ions to the POMs' surface. Band structure analysis suggests the photo-harvesting efficiency of the TiO2 core with the conduction band edge higher than the reduction potential of CuII/I and multi-electron CO2 reduction potentials. Photochemical CO2 reduction with Cux[POM]@TiO2 results in 30 µmol gcat. -1 CO (79 %) and 8 µmol gcat -1 of CH4 (21 %). Quasi-in-situ Raman study provides evidence in support of CO2 adsorption on the Cux[POM]@TiO2 surface. 13C and D2O labeling studies affirm the {Cu-[CO2]-} adduct formation. Despite the photo-harvesting ability of Nax[POM]@TiO2 itself, the poor CO2 adsorption ability of sodium ions highlights the crucial role of copper ion CO2 photo-reduction. Characterization of the {M-[η2-CO2]-} species via surface tuning validates the CO2 activation and photochemical reduction pathway proposed earlier.

Elucidating the Role of Atomically Dilute Copper Centers Impregnating a Phosphamide Polymer for the Preferential Hydrogen Evolution Reaction over CO2 Reduction.

Organic polymers have attracted considerable interest in designing a multifunctional electrocatalyst. However, the inferior electro-conductivity of such metal-free polymers is often regarded as a shortcoming. Herein, a nitrogen- and phosphorus-rich polymer with phosphamide functionality (PAP) in the repeating unit has been synthesized from diaminopyridine (DAP) and phenylphosphonic dichloride (PPDC) precursors. The presence of phosphamide oxygen and pyridine nitrogen in the repeating unit of PAP leads to the coordination of the CuII ion and the incorporation of 3.29 wt % in the polymer matrix (Cu30@PAP) when copper salt is used to impregnate the polymer. Combined with a spectroscopic, microscopic, and DFT study, the coordination and geometry of copper in the PAP matrix has been established to be a distorted square planar CuII in a N2O2 ligand environment where phosphamide oxygen and pyridine nitrogen of the PAP coordinate to the metal center. The copper incorporation in the PAP modulates its electrocatalytic activity. On the glassy carbon electrode, PAP shows inferior activity toward the hydrogen evolution reaction (HER) in 0.5 M H2SO4 while 3 wt % copper incorporation (Cu30@PAP) significantly improves the HER performance with an overpotential of 114 mV at 10 mA cm-2. The notable electrochemical activity with Cu30@PAP occurs due to the impregnation of Cu(II) in PAP, improved electro-kinetics, and better charge transfer resistance (Rct). When changing the electrolyte from H2SO4 to CO2-saturated bicarbonate solution at nearly neutral pH, PAP shows HER as the dominant pathway along with the partial reduction of CO2 to formate. Moreover, the use of Cu30@PAP as an electrolcatalyst could not alter the predominant HER path, and only 20% Faradaic efficiency for the CO2 reduced products has been achieved. Post-chronoamperometric characterization of the recovered catalyst suggests an unaltered valence state of the copper ion and the intact chemical structure of PAP. DFT studies unraveled that the copper sites of Cu30@PAP promote water adsorption while phosphamide-NH of the PAP can weakly hold the CO2 adduct via a hydrogen bonding interaction. A detailed calculation has pointed out that the tetra-coordinated copper centers present in the PAP frame are the reactive sites and that the formation of the [CuI-H] intermediate is the rate-limiting step for both HER and its competitive side reaction, i.e., CO2 reduction to formate or CO formation. The high proton concentration in the electrolyte of pH < 7 leads to HER as the predominant pathway. This combined experimental and theoretical study has highlighted the crucial role of copper sites in electrocatalysis, emphasizing the plausible reason for electrocatalytic selectivity.

Ionic γ-FeO(OH) Nanocrystal Stabilized by Small Isopolymolybdate Clusters as Reactive Core for Water Oxidation.

At near neutral to basic pH, hydrolysis-induced aggregation to insoluble bulk iron-oxide is often regarded as the pitfalls of molecular iron clusters. Iron-oxide nanocrystals are encouragingly active over the molecular clusters and/or bulk oxides albeit, stabilizing such nanostructures in aqueous pH and under turnover condition remain a perdurable challenge. Herein, an Anderson-type [Mo7 O24 ]6- isopolyanion, a small (dimension ca. 0.85 nm) isolable polyoxometalate (POM) possessing only {31} atoms, has been introduced for the first time as a covalent linker to stabilize an infinitely stable and aqueous-soluble γ-FeO(OH) nanocore. During the hydrothermal isolation of the material, a partial dissociation of the parent [Mo7 O24 ]6- may lead to the in situ generation of few analogous [Mox Oy ]n- clusters, proved by Raman study, which can also participate in stabilizing the γ-FeO(OH) nanocore, Mox Oy @FeO(OH). However, due to high ionic charge on {Mo=O} terminals of the [Mox Oy ]n- , they are covalently linked via MoVI -µ2 O-FeIII bridging to γ-FeO(OH) core in Mox Oy @FeO(OH), established by numerous spectroscopic and microscopic evidence. Such bonding mode is more likely as precedent from the coordination motif documented in the transition metal clusters stabilized by this POM. The γ-FeO(OH) nanocore of Mox Oy @FeO(OH) behaves as potent active center for electrochemical water oxidation with a overpotential, 263 mV @ 10 mA cm-2 , lower than that observed for bare γ-FeO(OH). Despite of some molybdenum dissolution from the POM ligands to the electrolyte, residual anionic POM fragments covalently bound to the OER active γ-FeO(OH) core of the Mox Oy @FeO(OH) makes the surface predominantly ionic that results in an ordered electrical double layer to promote a better charge transport across the electrode-electrolyte junction, less likely in bulk γ-FeO(OH).

Mechanistic Insights into the Appel Reaction Mediated by a Poly-Phosphamide Material as a Heterogeneous Catalyst.

Due to notable thermochemical stability, polyphosphamides are often regarded as flame retardants, while molecular phosphamides can serve as versatile Lewis base to catalyze diverse organic transformations. Being chemically analogous to phosphine oxide, phosphamide can also be considered as a mediator for the phosphine-mediated reaction. Herein, an amorphous polymeric material consisting of phosphamide (-NH-P(O)) in the repeating unit (POP) has been prepared via condensation of tris(2-aminoethyl)amine (TREN) and phenyl phosphinic dichloride (PPDC). The POP is isolated as a metal-free and pure organic material which is made of a strong covalent bond and the phosphamide unit is deployed in the organic framework. The presence of phosphamide in the repeating unit of the isolated amorphous POP material can be confirmed by 31P CPMAS NMR, FTIR, and Raman studies. The core-level N 2p and P 2p X-ray photoelectron spectra are in accordance with the presence of tertiary amine nitrogen attached to carbon and secondary amine nitrogen attached to phosphorus. Elemental analyses have depicted approximately 19.7% of phosphorus content in the material, which is being utilized to study the catalytic Appel reaction with 76% conversion of alcohol to a corresponding halide and TON of 462. Quasi in situ Raman study has identified that amino phosphine formed via in situ reduction of the phosphamide unit of the POP catalyzes the halogenation of primary and secondary alcohols with wide substrate scope and functional group tolerance. Kinetic studies have established a first-order dependence with respect to alcohol, while deuterium labeling experiments emphasize that the deprotonation of alcohol is the rate-limiting step. High thermal stability of the material, scope of easy catalyst recyclability, and a cumulative TON of 1386 have led the POP as an emerging pure organic material to be explored further for other phosphine-mediated organocatalysis.

Immobilization of Phosphamide on the TiO2 Surface for Heterogeneous Phase Catalytic Appel Reaction.

Global consumption of triphenylphosphine (Ph3P) for phosphorus-mediated organic synthesis and production of the dead-end triphenylphosphine oxide (Ph3PO) waste is exceptionally high. Recycling Ph3PO and/or use of it as a reaction mediator gained significant attention. On the other end, phosphamides, traditionally used as a flame redundant, are stable analogues to Ph3PO. Herein, via a low temperature condensation reaction of methyl 4-(aminomethyl)benzoate (AMB) and diphenyl phosphinic chloride (DPPC), methyl 4-((N,N-diphenylphosphinamido)methyl)benzoate (1) has been synthesized and hydrolysis of the ester functional group of 1 leads to a phosphamide with a carboxylate terminal, 4-((N,N-diphenylphosphinamido)methyl)benzoic acid (2). The presence of phosphamide functionality (NH─P═O) in 2 can be confirmed by its characteristic Raman vibration at 999 cm-1 with expected P-N and P═O bonds distances from the single-crystal X-ray structure. In-situ hydrolysis of [Ti(OiPr)4] in the presence of 2 followed by hydrothermal heating results in immobilization of 2 on a ca. 5 nm TiO2 surface (2@TiO2). The covalent attachment of 2 via coordination through the carboxylate terminal to the TiO2 nanocrystal's surface has been established via multiple spectroscopic and microscopic studies. 2@TiO2 is further used as the heterogeneous mediator for the catalytic Appel reaction, halogenation of alcohol (typically mediated by phosphine), with a fair catalytic conversion and a recorded TON up to 31. The major advantage of the heterogeneous approach studied herein is the recovery of used 2@TiO2 from the reaction mixture via centrifugation only leaving the organic product in the supernatant, which is limiting in Ph3P-mediated homogeneous catalysis. Time-resolved Raman spectroscopy confirms amino phosphine as the active species formed in-situ during the catalytic Appel reaction. Post-catalytic characterization of the material recovered after catalysis from the reaction mixture confirms the chemical integrity and that can further be utilized for another two catalytic runs. The developed reaction scheme showcases the use of a phosphamide as a reactive analogue to Ph3PO for an organic reaction in a heterogeneous approach, and the same strategy can be explored further as a general scheme for other phosphorus-mediated reactions.

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.

Electrochemically Derived Crystalline CuO from Covellite CuS Nanoplates: A Multifunctional Anode Material.

In the present era, electrochemical water splitting has been showcased as a reliable solution for alternative and sustainable energy development. The development of a cheap, albeit active, catalyst to split water at a substantial overpotential with long durability is a perdurable challenge. Moreover, understanding the nature of surface-active species under electrochemical conditions remains fundamentally important. A facile hydrothermal approach is herein adapted to prepare covellite (hexagonal) phase CuS nanoplates. In the covellite CuS lattice, copper is present in a mixed-valent state, supported by two different binding energy values (932.10 eV for CuI and 933.65 eV for CuII) found in X-ray photoelectron spectroscopy analysis, and adopted two different geometries, that is, trigonal planar preferably for CuI and tetrahedral preferably for CuII. The as-synthesized covellite CuS behaves as an efficient electro(pre)catalyst for alkaline water oxidation while deposited on a glassy carbon and nickel foam (NF) electrodes. Under cyclic voltammetry cycles, covellite CuS electrochemically and irreversibly oxidized to CuO, indicated by a redox feature at 1.2 V (vs the reversible hydrogen electrode) and an ex situ Raman study. Electrochemically activated covellite CuS to the CuO phase (termed as CuSEA) behaves as a pure copper-based catalyst showing an overpotential (η) of only 349 (±5) mV at a current density of 20 mA cm-2, and the TOF value obtained at η349 (at 349 mV) is 1.1 × 10-3 s-1. A low Rct of 5.90 Ω and a moderate Tafel slope of 82 mV dec-1 confirm the fair activity of the CuSEA catalyst compared to the CuS precatalyst, reference CuO, and other reported copper catalysts. Notably, the CuSEA/NF anode can deliver a constant current of ca. 15 mA cm-2 over a period of 10 h and even a high current density of 100 mA cm-2 for 1 h. Post-oxygen evolution reaction (OER)-chronoamperometric characterization of the anode via several spectroscopic and microscopic tools firmly establishes the formation of crystalline CuO as the active material along with some amorphous Cu(OH)2 via bulk reconstruction of the covellite CuS under electrochemical conditions. Given the promising OER activity, the CuSEA/NF anode can be fabricated as a water electrolyzer, Pt(-)//(+)CuSEA/NF, that delivers a j of 10 mA cm-2 at a cell potential of 1.58 V. The same electrolyzer can further be used for electrochemical transformation of organic feedstocks like ethanol, furfural, and 5-hydroxymethylfurfural to their respective acids. The present study showcases that a highly active CuO/Cu(OH)2 heterostructure can be constructed in situ on NF from the covellite CuS nanoplate, which is not only a superior pure copper-based electrocatalyst active for OER and overall water splitting but also for the electro-oxidation of industrial feedstocks.

Dioxygen Activation and Mandelate Decarboxylation by Iron(II) Complexes of N4 Ligands: Evidence for Dioxygen-Derived Intermediates from Cobalt Analogues.

The isolation, characterization, and dioxygen reactivity of monomeric [(TPA)MII(mandelate)]+ (M = Fe, 1; Co, 3) and dimeric [(BPMEN)2MII2(µ-mandelate)2]2+ (M = Fe, 2; Co, 4) (TPA = tris(2-pyridylmethyl)amine and BPMEN = N1,N2-dimethyl-N1,N2-bis(pyridin-2-yl-methyl)ethane-1,2-diamine) complexes are reported. The iron(II)- and cobalt(II)-mandelate complexes react with dioxygen to afford benzaldehyde and benzoic acid in a 1:1 ratio. In the reactions, one oxygen atom from dioxygen is incorporated into benzoic acid, but benzaldehyde does not derive any oxygen atom from dioxygen. While no O2-derived intermediate is observed with the iron(II)-mandelate complexes, the analogous cobalt(II) complexes react with dioxygen at a low temperature (-80 °C) to generate the corresponding cobalt(III)-superoxo species (S), a key intermediate implicated in the initiation of mandelate decarboxylation. At -20 °C, the cobalt(II)-mandelate complexes bind dioxygen reversibly leading to the formation of µ-1,2-peroxo-dicobalt(III)-mandelate species (P). The geometric and electronic structures of the O2-derived intermediates (S and P) have been established by computational studies. The intermediates S and P upon treatment with a protic acid undergo decarboxylation to afford benzaldehyde (50%) with a concomitant formation of the corresponding µ-1,2-peroxo-µ-mandelate-dicobalt(III) (P1) species. The crystal structure of a peroxide species isolated from the cobalt(II)-carboxylate complex [(TPA)CoII(MPA)]+ (5) (MPA = 2-methoxyphenylacetate) supports the composition of P1. The observations of the dioxygen-derived intermediates from cobalt complexes and their electronic structure analyses not only provide information about the nature of active species involved in the decarboxylation of mandelate but also shed light on the mechanistic pathway of two-electron versus four-electron reduction of dioxygen.

Beyond CO2 Reduction: Vistas on Electrochemical Reduction of Heavy Non-metal Oxides with Very Strong E-O Bonds (E = Si, P, S).

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 management. Besides CO2RR, there is an additional strong demand for benign electrochemical reduction of other important heavy non-metal oxo species (e.g., SiO2, phosphine oxides, SO2) with thermodynamically stable E-O bonds, which accrue in large quantities in industry. In this respect, the energy-intense deoxygenation of oxo compounds of silicon, phosphorus, and sulfur is of particular technological importance because they represent some of the main feedstocks to produce important molecules and functional materials. For example, the release of elemental silicon, phosphorus (P4), and sulfur (S8) from naturally occurring minerals (e.g., silicate, phosphate, sulfate) follows energy-intensive chemical routes. Thus, the established chemical reduction routes to deoxygenate such oxo precursors produce tons of reagent waste or, in the case of carbothermal treatment of minerals, afford a lot of CO2. On the contrary, electrochemical strategies developed for the selective deoxygenation of E-O compounds remain as a feasible alternative powered by renewable electricity instead of fossil energy. Moderate reaction conditions, a large scope in experiment design for selective reactions, easy product isolation, and zero reagent waste by applying electrochemical methods offer a promising solution to overcome the drawbacks of chemical reduction routes. This Perspective summarizes the emergence of electrochemical strategies developed for the reduction of selected examples of E-O/E═O compounds with E = silicon, phosphorus, and sulfur in the past few decades and highlights opportunities and future challenges.

A Systems Approach to a One-Pot Electrochemical Wittig Olefination Avoiding the Use of Chemical Reductant or Sacrificial Electrode.

An unprecedented one-pot fully electrochemically driven Wittig olefination reaction system without employing a chemical reductant or sacrificial electrode material to regenerate triphenylphosphine (TPP) from triphenylphosphine oxide (TPPO) and base-free in situ formation of Wittig ylides, is reported. Starting from TPPO, the initial step of the phosphoryl P=O bond activation proceeds through alkylation with RX (R=Me, Et; X=OSO2 CF3 (OTf)), affording the corresponding [Ph3 POR]+ X- salts which undergo efficient electroreduction to TPP in the presence of a substoichiometric amount of the Sc(OTf)3 Lewis acid on a Ag-electrode. Subsequent alkylation of TPP affords Ph3 PR+ which enables a facile and efficient electrochemical in situ formation of the corresponding Wittig ylide under base-free condition and their direct use for the olefination of various carbonyl compounds. The mechanism and, in particular, the intriguing role of Sc3+ as mediator in the TPPO electroreduction been uncovered by density functional theory calculations.

Visible-Light-Driven Water Oxidation with a Polyoxometalate-Complexed Hematite Core of 275†Iron Atoms.

Although metal oxide nanocrystals are often highly active, rapid aggregation (particularly in water) generally precludes detailed solution-state investigations of their catalytic reactions. This is equally true for visible-light-driven water oxidation with hematite α-Fe2 O3 nanocrystals, which bridge a conceptual divide between molecular complexes of iron and solid-state hematite photoanodes. We herein report that the aqueous solubility and remarkable stability of polyoxometalate (POM)-complexed hematite cores with 275 iron atoms enable investigations of visible-light-driven water oxidation at this frontier using the versatile toolbox of solution-state methods typically reserved for molecular catalysis. The use of these methods revealed a unique mechanism, understood as a general consequence of fundamental differences between reactions of solid-state metal oxides and freely diffusing "fragments" of the same material.

Reductive Activation of O2 by Non-Heme Iron(II) Benzilate Complexes of N4 Ligands: Effect of Ligand Topology on the Reactivity of O2-Derived Oxidant.

A series of iron(II) benzilate complexes (1-7) with general formula [(L)FeII(benzilate)]+ have been isolated and characterized to study the effect of supporting ligand (L) on the reactivity of metal-based oxidant generated in the reaction with dioxygen. Five tripodal N4 ligands (tris(2-pyridylmethyl)amine (TPA in 1), tris(6-methyl-2-pyridylmethyl)amine (6-Me3-TPA in 2), N1,N1-dimethyl-N2,N2-bis(2-pyridylmethyl)ethane-1,2-diamine (iso-BPMEN in 3), N1,N1-dimethyl-N2,N2-bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me2-iso-BPMEN in 4), and tris(2-benzimidazolylmethyl)amine (TBimA in 7)) along with two linear tetradentate amine ligands (N1,N2-dimethyl-N1,N2-bis(2-pyridylmethyl)ethane-1,2-diamine (BPMEN in 5) and N1,N2-dimethyl-N1,N2-bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me2-BPMEN in 6)) were employed in the study. Single-crystal X-ray structural studies reveal that each of the complex cations of 1-3 and 5 contains a mononuclear six-coordinate iron(II) center coordinated by a monoanionic benzilate, whereas complex 7 contains a mononuclear five-coordinate iron(II) center. Benzilate binds to the iron center in a monodentate fashion via one of the carboxylate oxygens in 1 and 7, but it coordinates in a bidentate chelating mode through carboxylate oxygen and neutral hydroxy oxygen in 2, 3, and 5. All of the iron(II) complexes react with dioxygen to exhibit quantitative decarboxylation of benzilic acid to benzophenone. In the decarboxylation pathway, dioxygen becomes reduced on the iron center and the resulting iron-oxygen oxidant shows versatile reactivity. The oxidants are nucleophilic in nature and oxidize sulfide to sulfoxide and sulfone. Furthermore, complexes 2 and 4-6 react with alkenes to produce cis-diols in moderate yields with the incorporation of both the oxygen atoms of dioxygen. The oxygen atoms of the nucleophilic oxidants do not exchange with water. On the basis of interception studies, nucleophilic iron(II) hydroperoxides are proposed to generate in situ in the reaction pathways. The difference in reactivity of the complexes toward external substrates could be attributed to the geometry of the O2-derived iron-oxygen oxidant. DFT calculations suggest that, among all possible geometries and spin states, high-spin side-on iron(II) hydroperoxides are energetically favorable for the complexes of 6-Me3-TPA, 6-Me2-iso-BPMEN, BPMEN, and 6-Me2-BPMEN ligands, while high spin end-on iron(II) hydroperoxides are favorable for the complexes of TPA, iso-BPMEN, and TBimA ligands.

Mimicking the Aromatic-Ring-Cleavage Activity of Gentisate-1,2-Dioxygenase by a Nonheme Iron Complex.

Gentisate-1,2-dioxygenase (GDO), a nonheme iron enzyme in the cupin superfamily, catalyzes the cleavage of the aromatic-ring of 2,5-dihydroxybenzoic acid (gentisic acid) to form maleylpyruvic acid in the microbial aerobic degradation of aromatic compounds. To develop a functional model of GDO, we have isolated a nonheme iron(II) complex, [(TpPh2 )FeII (DHN-H)] (TpPh2 =hydrotris(3,5-diphenylpyrazole-1-yl)borate, DHN-H=1,4-dihydroxy-2-naphthoate). In the reaction with O2 , the biomimetic complex oxidatively cleaves the aromatic ring of the coordinated substrate with the incorporation of both the oxygen atoms from molecular oxygen into the cleavage product. The presence of para-hydroxy group on the substrate plays a crucial role in directing the aromatic-ring cleaving reaction.

Reactivity of biomimetic iron(II)-2-aminophenolate complexes toward dioxygen: mechanistic investigations on the oxidative C-C bond cleavage of substituted 2-aminophenols.

The isolation and characterization of a series of iron(II)-2-aminophenolate complexes [(6-Me3-TPA)Fe(II)(X)](+) (X = 2-amino-4-nitrophenolate (4-NO2-HAP), 1; X = 2-aminophenolate (2-HAP), 2; X = 2-amino-3-methylphenolate (3-Me-HAP), 3; X = 2-amino-4-methylphenolate (4-Me-HAP), 4; X = 2-amino-5-methylphenolate (5-Me-HAP), 5; X = 2-amino-4-tert-butylphenolate (4-(t)Bu-HAP), 6 and X = 2-amino-4,6-di-tert-butylphenolate (4,6-di-(t)Bu-HAP), 7) and an iron(III)-2-amidophenolate complex [(6-Me3-TPA)Fe(III)(4,6-di-(t)Bu-AP)](+) (7(Ox)) supported by a tripodal nitrogen ligand (6-Me3-TPA = tris(6-methyl-2-pyridylmethyl)amine) are reported. Substituted 2-aminophenols were used to prepare the biomimetic iron(II) complexes to understand the effect of electronic and structural properties of aminophenolate rings on the dioxygen reactivity and on the selectivity of C-C bond cleavage reactions. Crystal structures of the cationic parts of 5·ClO4 and 7·BPh4 show six-coordinate iron(II) centers ligated by a neutral tetradentate ligand and a monoanionic 2-aminophenolate in a bidentate fashion. While 1·BPh4 does not react with oxygen, other complexes undergo oxidative transformation in the presence of dioxygen. The reaction of 2·ClO4 with dioxygen affords 2-amino-3H-phenoxazin-3-one, an auto-oxidation product of 2-aminophenol, whereas complexes 3·BPh4, 4·BPh4, 5·ClO4 and 6·ClO4 react with O2 to exhibit C-C bond cleavage of the bound aminophenolates. Complexes 7·ClO4 and 7(Ox)·BPh4 produce a mixture of 4,6-di-tert-butyl-2H-pyran-2-imine and 4,6-di-tert-butyl-2-picolinic acid. Labeling experiments with (18)O2 show the incorporation of one oxygen atom from dioxygen into the cleavage products. The reactivity (and stability) of the intermediate, which directs the course of aromatic ring cleavage reaction, is found to be dependent on the nature of ring substituent. The presence of two tert-butyl groups on the aminophenolate ring in 7·ClO4 makes the complex slow to cleave the C-C bond of 4,6-di-(t)Bu-HAP, whereas 4·BPh4 containing 4-Me-HAP displays fastest reactivity. Density functional theory calculations were conducted on [(6-Me3-TPA)Fe(III)(4-(t)Bu-AP)](+) (6(Ox)) to gain a mechanistic insight into the regioselective C-C bond cleavage reaction. On the basis of the experimental and computational studies, an iron(II)-2-iminobenzosemiquinonate intermediate is proposed to react with dioxygen resulting in the oxidative C-C bond cleavage of the coordinated 2-aminophenolates.

Surface Structure to Tailor the Electrochemical Behavior of Mixed-Valence Copper Sulfides during Water Electrolysis.

The semiconducting behavior of mixed-valence copper sulfides arises from the pronounced covalency of Cu-S bonds and the exchange coupling between CuI and CuII centers. Although electrocatalytic study with digenite Cu9S5 and covellite CuS has been performed earlier, detailed redox chemistry and its interpretation through lattice structure analysis have never been realized. Herein, nanostructured Cu9S5 and CuS are prepared and used as electrode materials to study their electrochemistry. Powder X-ray diffraction (PXRD) and microscopic studies have found the exposed surface of Cu9S5 to be d(0015) and d(002) for CuS. Tetrahedral (Td) CuII, distorted octahedral (Oh) CuII, and trigonal planar (Tp) CuI sites form the d(0015) surface of Cu9S5, while the (002) surface of CuS consists of only Td CuII. The distribution of CuI and CuII sites in the lattice, predicted by PXRD, can further be validated through core-level Cu 2p X-ray photoelectron spectroscopy (XPS). The difference in the electrochemical response of Cu9S5 and CuS arises predominantly from the different copper sites present in the exposed surfaces and their redox states. In situ Raman spectra recorded during cyclic voltammetric study indicates that Cu9S5 is more electrochemically labile compared to CuS and transforms rapidly to CuO/Cu2O. Contact-angle and BET analyses imply that a high-surface-energy and macroporous Cu9S5 surface favors the electrolyte diffusion, which leads to a pronounced redox response. Post-chronoamperometric (CA) characterizations identify the potential-dependent structural transformation of Cu9S5 and CuS to CuO/Cu2O/Cu(OH)2 electroactive species. The performance of the in situ formed copper-oxides towards electrocatalytic water-splitting is superior compared to the pristine copper sulfides. In this study, the redox chemistry of the Cu9S5/CuS has been correlated to the atomic arrangements and coordination geometry of the surface exposed sites. The structure-activity correlation provides in-depth knowledge of how to interpret the electrochemistry of metal sulfides and their in situ potential-driven surface/bulk transformation pathway to evolve the active phase.

Vacancy-Rich SnO2 Quantum Dot Stabilized by Polyoxomolybdate as Electrocatalyst for Selective NH3 Production.

The pronounced conductivity of tin dioxide (SnO2) nanoparticles makes it an ideal multifunctional electrode material, while the challenge is to stabilize the quantum dot (QD) SnO2 nanocore in water. An Anderson-type polyoxomolybdate, (NH4)6[Mo7O24], is employed as an inorganic ligand to stabilize a ca. 6 nm SnO2 QD (Mox@SnO2). X-ray scattering and diffraction studies confirm the tetragonal SnO2 nanocore in Mox@SnO2. Elemental analyses are in good agreement with the mass spectrometric detection of the [Mo7O24]6- cluster present in Mox@SnO2. The ionic POMs attached to the SnO2 surface through [Mo-O-Sn] covalent linkages have been established by surface zeta potential, shift of the [Mo = O]t Raman vibration, and extended X-ray absorption fine structure (EXAFS) analyses. The presence of the [Mo7O24]6- cluster in the Mox@SnO2 is responsible for the remarkable aqueous stability of Mox@SnO2 in the pH range of 3-9. Dominant oxygen vacancy in the SnO2 core, identified by EXAFS data and the anisotropic electron paramagnetic resonance (EPR) signals (g ∼ 2.4 and 1.9), results in facile electronic conduction in Mox@SnO2 while being deposited on the electrode surface. Mox@SnO2 acts as an active catalyst for the electrocatalytic nitrate reduction (eNOR) to ammonia with 94% faradaic efficiency (FE) at -0.2 V vs RHE and a yield rate of 28.9 mg h-1 cm-2. The stability of Mox@SnO2 in acidic pH provides scope to reuse the Mox@SnO2 electrode at least four times with notable NH3 selectivity and a superior production rate (239.06 mmol g-1(cat) h-1). This study demonstrates the essential role of POM in stabilizing SnO2 QD, harnessing its electrochemical activity toward electrocatalytic ammonia production.

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.

Evolution of Mn-Bi2O3 from the Mn-doped Bi3O4Br electro(pre)catalyst during the oxygen evolution reaction.

Mn-doped Bi3O4Br has been synthesized using a solvothermal route. The undoped Bi3O4Br and Mn-Bi3O4Br materials possess orthorhombic unit cells with two distinct Bi sites forming a layered atomic arrangement. The shift in the (020) plane in the powder X-ray diffraction (PXRD) pattern confirms Mn-doping in the Bi3O4Br lattice. Elemental mapping indicated 7% Mn doping in the Bi3O4Br lattice structure. A core-level X-ray photoelectron study (XPS) indicates the presence of BiIII and MnII valence-states in Mn-Bi3O4Br. Doping with a cation (MnII) containing a different charge and ionic radius resulted in vacancy/defects in Mn-Bi3O4Br which further altered its electronic structure by reducing the indirect band gap, beneficial for electron conduction and electrocatalysis. The irreversible MnII to MnIII transformation at a potential of 1.48 V (vs. RHE) precedes the electrochemical oxygen evolution reaction (OER). The Mn-doped electrocatalyst achieved 10 mA cm-2 current density at 337 mV overpotential, while the pristine Bi3O4Br required 385 mV overpotential to reach the same activity. The pronounced OER activity of the Mn-Bi3O4Br sample over the pristine Bi3O4Br highlights the necessity of MnII doping. The superior activity of the Mn-Bi3O4Br catalyst over that of Bi3O4Br is due to a low Tafel slope, better double-layer capacitance (Cdl), and small charge-transfer resistance (Rct). The chronoamperometry (CA) study depicts long-term stability for 12 h at 20 mA cm-2. An electrolyzer fabricated as Pt(-)/(+)Mn-Bi3O4Br can deliver 10 mA cm-2 at a cell potential of 2.05 V. The post-CA-OER analyses of the anode confirmed the leaching of [Br-] followed by in situ formation of Mn-doped Bi2O3 as the electrocatalytically active species. Herein, an ultra-low Mn-doping into Bi3O4Br leads to an improvement in the electrocatalytic performance of the inactive Bi3O4Br material.

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).

Ease of Electrochemical Arsenate Dissolution from FeAsO4 Microparticles during Alkaline Oxygen Evolution Reaction.

Transition metal-based ABO4-type materials have now been paid significant attention due to their excellent electrochemical activity. However, a detailed study to understand the active species and its electro-evolution pathway is not traditionally performed. Herein, FeAsO4, a bimetallic ABO4-type oxide, has been prepared solvothermally. In-depth microscopic and spectroscopic studies showed that the as-synthesized cocoon-like FeAsO4 microparticles consist of several small individual nanocrystals with a mixture of monoclinic and triclinic phases. While depositing FeAsO4 on three-dimensional nickel foam (NF), it can show oxygen evolution reaction (OER) in a moderate operating potential. During the electrochemical activation of the FeAsO4/NF anode through cyclic voltammetric (CV) cycles prior to the OER study, an exponential increment in the current density (j) was observed. An ex situ Raman study with the electrode along with field emission scanning electron microscopy imaging showed that the pronounced OER activity with increasing number of CV cycles is associated with a rigorous morphological and chemical change, which is followed by [AsO4]3- leaching from FeAsO4. A chronoamperometric study and subsequent spectro- and microscopic analyses of the isolated sample from the electrode show an amorphous γ-FeO(OH) formation at the constant potential condition. The in situ formation of FeO(OH)ED (ED indicates electrochemically derived) shows better activity compared to pristine FeAsO4 and independently prepared FeO(OH). Tafel, impedance spectroscopic study, and determination of electrochemical surface area have inferred that the in situ formed FeO(OH)ED shows better electro-kinetics and possesses higher surface active sites compared to its parent FeAsO4. In this study, the electrochemical activity of FeAsO4 has been correlated with its structural integrity and unravels its electro-activation pathway by characterizing the active species for OER.