Ni Oxidation State Research Articles

Improving electrocatalytic OER activity of perovskites through insertion of ternary B-site metals

Anion exchange membrane water electrolysers (AEMWEs) demonstrate promise for efficient and cost-effective hydrogen production. However, the sluggish kinetics of the oxygen evolution reaction (OER) hinder their deployment, requiring the development of cheap and efficient electrocatalysts. In this work, lanthanum nickelate-based perovskites have been prepared via sol-gel synthesis and modified with ternary Co and Mn B-site metals, increasing their catalytic activity. X-ray diffraction (XRD) data indicates that a rhombohedral crystal structure has been achieved, with strain increasing as the percentage of ternary metal increases. The best performing cobalt-doped material, with a Ni:Fe:Co atomic ratio of 6:2:2, displayed a Tafel slope of 38.4 mV dec−1, with an OER overpotential of 348 mV at 10 mA cm−2, while the best performing manganese-doped material had a Ni:Fe:Mn atomic ratio of 8:1.5:0.5 and achieved 10 mA cm−2 at an OER overpotential of 361 mV and a Tafel slope of 42.7 mV dec−1. Electrochemical surface area (ECSA) calculations and particle size analysis suggest that the surface area and physical structure of the materials is not the most influential factor in determining catalytic activity; rather, electronic structure appears to play a defining role. XPS analysis has shown that both Co- and Mn-doped catalysts with an average Fe oxidation state around 2.5 and average Ni oxidation state around 2.4 demonstrate the best performance, likely due to an increased number of oxygen vacancies, which are necessary for achieving charge neutrality within the perovskite structure. Furthermore, ternary metal insertion results in a negative shift in the Ni2+ binding energy, facilitating electrochemical oxidation of Ni(II) to Ni(III), which is an essential prerequisite to the OER.

Effects of nickel-deactivations on zeolites-Y of different SiO2/Al2O3 ratios in catalytic cracking of hydrocarbons

Effects of nickel deactivation on catalytic activities of three types of zeolites-Y (Y-5.1, USY-5.2, and VUSY-12) with varying SiO2/Al2O3 ratios were studied in cracking of hydrocarbons. Physicochemical characteristics such as crystalline phases, Ni oxidation states, morphology, acidity, surface area, and thermal stability of the samples were analysed. XRD revealed the absence of observable nickel compounds below 5 wt%, with NiO phase emerging at higher concentrations. Surface areas decreased from 826 to 615 m2/g (Y-5.1), 786–686 m2/g (USY-5.2), and 762–571 m2/g (VUSY-12) at 30 wt% Ni. The total acid sites also reduced from 17.247 to 9.826 µmol/g (Y-5.1), 15.464–8.854 µmol/g (USY-5.2), and 7.094–4.876 µmol/g (VUSY-12). XPS confirmed Ni2+ states. Catalytic cracking tests using n-Heptane demonstrated increases in C5-C6 alkanes, olefins, hydrogen, and methane yields as nickel concentration increased, with respective values of 64 %, 28 %, 79 % and 68 % for Y-5.1; 62 %, 28 %, 76 %, and 62 % for USY-5.2; and 58 %, 21 %, 75 %, and 60 % for VUSY-12. A corresponding decrease in heavier components were observed. The study demonstrates that nickel modification significantly impacts the physicochemical properties and catalytic performance of zeolite-Y and these depend strongly on the SiO2/Al2O3 ratios. The study gives further insights into the structural and catalytic modifications induced by nickel doping in zeolites, highlighting the potential of nickel-modified zeolites in promoting undesirable hydrogen and gas.

X-ray spectromicroscopy of single NiO antiferromagnetic nanoparticles

The chemical and magnetic properties of NiO nanoparticles (NP) have been studied with single-particle sensitivity by means of synchrotron-based, polarization-dependent X-ray absorption spectroscopy using photoemission electron microscopy around the Ni L3,2 edges. Three samples of NP in a size range of 40-120 nm were synthesized by thermal decomposition and subsequent calcination processes. The analysis of the local X-ray absorption spectra of tens of individual NP indicates a strong dependence of their Ni oxidation state with the calcination protocol of each sample. Additional electron-microscopy-based images and spectra of a few individual NP as well as other standard macroscopic data are in very good agreement with these experimental findings. These results showcase the relevance of combining standard and advanced single-particle studies to gain further insight into the understanding and control of electronic and magnetic phenomena at the nanoscale.

Strengthened Removal of Tetracycline by a Bi/Ni Co-Doped SrTiO3/TiO2 Composite under Visible Light

A two-step hydrothermal method was used to first obtain a SrTiO3/TiO2 composite then to dope the composite with Bi, Ni and Bi/Ni. Morphology, crystalline structures, surface valances and optical features of SrTiO3/TiO2 and Bi-, Ni-, Bi/Ni-doped SrTiO3/TiO2 were assessed. XRD and XPS analysis showed that Bi and Ni were successfully doped and existed in Bi(3+) and Ni(2+) oxidation state. UV–vis analysis further revealed that the bandgap energies of TiO2 and SrTiO3/TiO2 were calculated to be 3.14 eV and 3.04 eV. By comparison, Bi, Ni and Bi/Ni doping resulted in the narrowing of bandgaps to 2.82 eV, 2.96 eV and 2.69 eV, respectively. The removal ability of SrTiO3/TiO2 and doped SrTiO3/TiO2 were investigated with tetracycline as the representative pollutant. After 40 min of exposure to visible light, Bi/Ni co-doped SrTiO3/TiO2 photocatalyst was able to remove 90% of the tetracycline with a mineralization rate of about 70%. In addition, first-order removal rate constant was 0.0074 min−1 for SrTiO3/TiO2 and increased to 0.0278 min−1 after co-doping. The strengthened removal by co-doped photocatalyst was attributed mainly to the enhanced absorption of visible light as co-doping resulted in the decreases of bandgap energies. At the same time, the co-doped material was robust against changes in pH. Removal of tetracycline was stable as pH changed from 5 to 9. Tetracycline removal was inhibited to a certain degree by the presence of nitrate, phosphate and high concentration of humic acid. Moreover, the co-doped material exhibited strong structural stability and reusability. In addition, a photocatalysis mechanism with photogenerated holes and ·O2− radicals as main oxidative species was proposed based on entrapping experiments and EPR results.

Mechanism of Nitrous Oxide Activation in C(sp2)-O Bond Formation Reactions Catalyzed by Nickel Complexes.

Recent groundbreaking experimental reports demonstrated that Ni complexes bearing a bidentate- or tridentate-bipyridine-based ligand can be used to activate N2O for use as an O-transfer agent in C(sp2)-O bond formation reactions under mild experimental conditions. In this work, quantum chemical calculations are used to shed light on the mechanism through which such metal complexes catalytically activate nitrous oxide, providing new fundamental insights into the development of novel catalysts for N2O revalorization. As a case study, we consider the recent work by Cornella and co-workers (Nature, 2022, 604, 677) concerning the synthesis of phenols from aryl halides at room temperature, which requires the use of an external reducing agent. Our results suggest that the metal center remains in its Ni(II) oxidation state throughout the whole catalytic cycle, despite the presence of various redox steps in the mechanism and the Ni ability to maneuver between a number of oxidation states. This counterintuitive behavior is made possible by the ligand redox activity in the catalytic process, which involves accepting electrons from the reducing agent. Several possible pathways are systematically investigated, each associated with distinct activation modes, kinetics, and reaction outcomes. The governing factors in dictating the preferred path lie in the electronic nature of the ligand (strong vs weak field) and its geometric structure (specifically, the number of coordinating arms). These characteristics play a pivotal role in determining whether the process follows a catalytic or stoichiometric route and can be in principle modulated for the design of new metal complexes with tailored redox properties and reactivity.

Mechanistic study of alkene hydrogenation catalyzed by cationic Ni(II)-hydride PNHP complexes – Ni(II/IV) vs. Ni(II) cycle

The hydrogenation mechanisms of alkenes catalyzed by square-planar cationic Ni(II)-PNHP hydride complexes have been computed (M06L-GD3-SCRF). It is found that the reaction prefers a non-bifunctional inner-sphere mechanism, the Ni(II)/Ni(IV) cycle involving H2 oxidative addition forming unusual Ni(IV) oxidation state and reductive elimination is accessible and has been proven to be superior or competitive with the widely accepted Ni(II) cycle undergoing concerted H2 σ-bond metathesis in formal Ni(II) oxidation state. Systematic investigations into the electronic and geometric effects of phosphine ligand substituents uncover their significant influence on the Gibbs free energy barrier of elementary steps, leading to differences in catalytic activity. Analysis into these effects demonstrates a strong correlation between the apparent free energy barrier and frontier orbital energy, natural charge of Ni-center and buried volume ratio of the catalyst. These findings offer valuable insights for the design of future catalysts.

Nickel(II) complexes with 14-membered bis-thiosemicarbazide and bis-isothiosemicarbazide ligands: synthesis, characterization and catalysis of oxygen evolution reaction.

Design and development of novel, low-cost and efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media is crucial for lowering the reaction overpotential and thus decreasing the energy input during the water electrolysis process. Herein, we present the synthesis of new 14-membered bis-thiosemicarbazide and bis-isothiosemicarbazide macrocycles and their nickel(II) complexes characterized by spectroscopic techniques (1H and 13C NMR, IR, UV-vis), electrospray ionization mass spectrometry, single crystal X-ray diffraction, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) and cyclic voltammetry. Finally, the activity of nickel(II) complexes towards OER is reported. NiIILSEt delivered a current density of 10 mA cm-2 at the lowest overpotential of 350 mV with the lowest Tafel slope of 93 mV dec-1. The high performance of NiIILSEt might be attributed to its high surface area and thus abundant active sites with the observed low charge-transfer resistance enabling the effective current flow through the electrocatalyst. Square-planar coordination geometry and increment in Ni oxidation state are believed to favor its OER performance. Beside high activity towards OER, NiIILSEt demonstrated excellent long-term stability with continuous operation, advocating its possible application in commercial systems.

Nickel-Catalyzed O-Arylation of Primary or Secondary Aliphatic Alcohols with (Hetero)aryl Chlorides: A Comparison of Ni(I) and Ni(II) Precatalysts.

A comparative experimental and computational study examining the interplay of the ancillary ligand structure and Ni oxidation state in the Ni-catalyzed C(sp2)-O cross-coupling of (hetero)aryl chlorides and primary or secondary aliphatic alcohols is presented, focusing on PAd-DalPhos (L1)-, CyPAd-DalPhos (L2)-, PAd2-DalPhos (L3)-, and DPPF (L4)-ligated [(L)NiCl]n (n = 1 or 2) and (L)Ni(o-tol)Cl precatalysts. Both L1 and L2 were found to outperform the other ligands examined, with the latter proving to be superior overall. While Ni(II) precatalysts generally outperformed Ni(I) species, in some instances the catalytic abilities of Ni(I) precatalysts were competitive with those of Ni(II). Density-functional theory calculations indicate the favorability of a Ni(0)/Ni(II) catalytic cycle featuring turnover-limiting C-O bond reductive elimination over a Ni(I)/Ni(III) cycle involving turnover-limiting C-Cl oxidative addition.

Evidence of hydrogen content and monovalent Ni oxidation state in non-superconducting bulk anchored infinite-layer nickelates

Evidence of hydrogen content and monovalent Ni oxidation state in non-superconducting bulk anchored infinite-layer nickelates

Morphology control of high-quality hexagonal perovskite BaNiO3 by molten salt method

BaNiO3 single crystals with a hexagonal perovskite structure are prized for their exceptional Ni oxidation state and face-sharing structure, which grants them a high-performance potential as electrocatalysts. Despite their potential, obtaining high-quality morphology of BaNiO3 single crystals remains a challenge, making their characterization difficult and limiting their efficiency. In this study, we present a method for synthesizing high-quality BaNiO3 single crystals by morphology control using a molten salt method, which involves modifying the concentration of KOH, reaction time, and cooling rate. The optimal conditions for synthesizing high-quality BaNiO3 single crystals were found to be a reactant-to-KOH ratio of 1:50 and a reaction time of more than 3 h, which resulted in hexagonal-prism-shaped single crystals. However, using different reactant-to-salt ratios and shorter reaction times led to the formation of polycrystalline or pine-needle-shaped BaNiO3 along with secondary phases of BaCO3 and NiO. A higher KOH concentration required a longer reaction time, as the precursor diffusion rate slowed down. The average size of BaNiO3 single crystals increased as the cooling rate decreased, reaching the average width of ∼90 μm and the length of over 1 mm at the cooling rate of 5 °C/h. Our findings present optimal conditions for synthesizing a high-quality single-crystalline BaNiO3 with a hexagonal perovskite structure and could contribute to the development of BaNiO3 crystals for applications in ferroelectrics, photovoltaics, and chemical catalysis.

24 Safe-by-Design Guidance for Multicomponent Nanostructured Materials (MCNM): Heavy Metals Containing Perovskites

Abstract Industry develops increasingly complex and advanced materials while incorporating the Safe-by-Design (SbD) concept into the R&D goals. Within HARMLESS (EU H2020), we use concepts of similarity for the risk screening during the SbD iterations. We rely predominantly on Novel Approach Methodologies (NAMs) due to ethical reasons, speed and parallel testing of several SbD versions. In general, aerosolization of nanostructured materials leading to inhalation of respirable fraction is considered one of the most important routes of exposure. Depending on the physicochemical properties of the materials, MCNM may either dissolve or persist within the lung. We selected in chimico NAMs (i.e., biodissolution in lung simulant fluids and surface reactivity assay) to understand how the properties of six different perovskites, intended to be used in the automotive catalysis sector, are connected to inhalation hazard endpoints. They all share a common concern: Co and Ni (heavy metals) in the structure. We found that the composition and surface properties play an important role in determining the particles fate upon inhalation, influencing metals bioavailability and the induced oxidative damage. At pH 7.5 and 4.5 simulant fluids, both relevant for pulmonary clearance, dissolution depended minimally on the noble metal doping but rather on the %weight of heavy metal in the structure. Furthermore, high surface reactivity was observed for all perovskites. Interestingly, the induced oxidative damage was correlating with the Ni %weight, surface thickness and Ni oxidation state. The results allowed us to rank different SbD versions against benchmarks, providing Safe-by-Design guidance on multicomponent, heavy metals-containing perovskites.

Unveiling Strong Ion-Electron-Lattice Coupling and Electronic Antidoping in Hydrogenated Perovskite Nickelate.

Despite being highly promising for applications in emergent electronic devices, decoding both the ion-electron-lattice coupling in correlated materials at the atomic scale and the electronic band structure remains a big challenge due to the strong and complex correlation among these degrees of freedom. Here, taking an epitaxial thin film of perovskite nickelate NdNiO3 as a model system, hydrogen-ion-induced giant lattice distortion and enhanced NiO6 octahedra tilting/rotation are demonstrated, which leads to a new robust hydrogenated HNdNiO3 phase with lattice expansion larger than 10% on a series of substrates. Moreover, under the effect of ion-electron synergistic doping, it is found that the proposed electronic antidoping, i.e., the doped electrons mainly fill the ground-state oxygen 2p holes instead of changing the Ni oxidation state from Ni3+ to Ni2+ , dominates the metal-insulator transition. Meanwhile, lattice modification with enhanced Ni-O-Ni bond tilting or rotation mainly modifies the orbital density of states near the Fermi level. Last, by electric-field-controlled hydrogen-ion intercalation and its strong coupling to the lattice and electron charge, selective micrometer-scale patterns with distinct structural and electronic states are fabricated. The results provide direct evidence for a strong ion-electron-lattice coupling in correlated physics and exhibit its potential applications in designing novel materials and devices.

Unveiling the role of multifunctional framework for high-energy P2-Na0.8Li0.12Ni0.22Mn0.66O2 cathode materials

Enhancing the interfacial stability between cathode active material and liquid/solid electrolyte is a vital step toward the development of high energy density sodium-ion batteries (SIBs). One of the challenges plaguing this field is an economical and feasible method to construct valid protective layers on cathode materials. Herein, an effective strategy based on synergetic effect of multifunctional framework by simultaneous surface NaTi2(PO4)3 (NTP) coating and bulk Ti4+ doping is designed to improve the performance of P2-Na0.8Li0.12Ni0.22Mn0.66O2 ([email protected]). The combined analysis of in-situ X-ray diffraction (in-situ XRD), scanning transmission electron microscopy (STEM) and density functional theory (DFT) calculations demonstrates that the multifunctional framework optimizes the lattice structure, improves the Ni oxidation states and enhances the stability of crystal and interfacial structure. [email protected] cathode displays high average discharge potential and fast diffusion of Na-ions and electrons. As a result, the [email protected] cathode reveals highly Na storage performance in both liquid-state and solid-state SIBs. The excellent capacity retentions after 500 cycles at 5 C in liquid-state batteries and after 100 cycles at 1 C in solid-state batteries are both close to 100%.

Thermal Methane Conversion to Formaldehyde Mediated by NiAlO3+ in the Gas Phase.

Understanding the active sites and reaction mechanisms of Ni-based catalysts, such as Ni/Al2O3, toward methane is a prerequisite for improving their rational design. Here, the gas-phase reactivity of NiAlO3+ cations toward CH4 is studied using mass spectrometry combined with density functional theory. Similar to our previous study on NiAl2O4+, we find evidence for the formation of both the methyl radical (CH3•) and formaldehyde (CH2O). The first step for methane activation is hydrogen atom abstraction by the terminal oxygen radical Ni(O)2AlO• from methane forming a [Ni(O)2AlOH+, •CH3] complex and leaving the Ni-oxidation state unchanged. The second C-H bond is subsequently activated by the association of a bridged Ni-O2--Al. The oxidation state of the Ni atom is reduced from +3 to +1 during the formation of formaldehyde. Compared to Al2O3+/CH4 and YAlO3+/CH4 systems, the Ni-atom substitution increases the overall reaction rate by roughly an order of magnitude and yields a CH3•/CH2O branching ratio of 0.62/0.38. The present study provides molecular-level insights into the highly efficient gas-phase reaction mechanism contributing to an improved understanding of methane conversion by Ni/Al2O3 catalysts.

The Role of the Redox Non-Innocent Hydroxyl Ligand in the Activation of O2 Performed by [Ni(H)(OH)

The cationic complex [Ni(H)(OH)]+ was previously found to activate dioxygen and methane in gas phase under single collision conditions. These remarkable reactivities were thought to originate from a non-classical electronic structure, where the Ni-center adopts a Ni(II), instead of the classically expected Ni(III) oxidation state by formally accepting an electron from the hydroxo ligand, which formally becomes a hydroxyl radical in the process. Such radicaloid oxygen moieties are envisioned to easily react with otherwise inert substrates, mimicking familiar reactivities of free radicals. In this study, the reductive activation of dioxygen by [Ni(H)(OH)]+ to afford the hydroperoxo species was investigated using coupled cluster, multireference ab initio and density functional theory calculations. Orbital and wave function analyses indicate that O2 binding tranforms the aforementioned non-classical electronic structure to a classical Ni(III)-hydroxyl system, before O2 reduction takes place. Remarkably, we found no evidence for a direct involvement of the radicaloid hydroxyl in the reaction with O2 , as is often assumed. The function of the redox non-innocent character of the activator complex is to protect the reactive electronic structure until the complex engages O2 , upon which a dramatic electronic reorganization releases internal energy and drives the chemical reaction to completion.

Reversible and Irreversible Cation Intercalation in NiFeOxOxygen Evolution Catalysts in Alkaline Media

For electrocatalysts with a layered structure, ion intercalation is a common phenomenon. Gaining reliable information about the intercalation of ions from the electrolyte is indispensable for a better understanding of the catalytic performance of these electrocatalysts. Here, we take a holistic approach for following intercalation processes by studying the dynamics of the catalyst, water molecules, and ions during intercalation using operando soft X-ray absorption spectroscopy (XAS). Sodium and oxygen K-edge and nickel L-edge spectra were used to investigate the Na+ intercalation in a Ni0.8Fe0.2Ox electrocatalyst during the oxygen evolution reaction (OER) in NaOH (0.1 M). The Na K-edge spectra show an irreversible intensity increase upon initial potential cycling and a reversible intensity increase at the intercalation potential, 1.45 VRHE, coinciding with an increase in the Ni oxidation state. Simultaneously, the O K-edge spectra show that the Na+ intercalation does not significantly impact the hydration of the catalyst.

Investigation of Structural and Electronic Changes Induced by Postsynthesis Thermal Treatment of LiNiO2

Postsynthesis thermal treatments at various temperatures in air have been applied to LiNiO2, and the induced structural and electronic changes have been uncovered. Except for the familiar decomposition process at higher temperatures, a series of transformations also take place under mild conditions. To identify such subtle changes, ex situ and in situ synchrotron radiation diffraction, ex situ 7Li nuclear magnetic resonance spectroscopy, and ex situ measurements of magnetic properties have been performed. We show that the reaction between LiNiO2 and CO2 starts already at a temperature of 200 °C, forming Li1–zNi1+zO2 layers. If the thickness of this layer is well adjusted, the electrochemical performance of LiNO2 can be improved. A cation off-stoichiometry of [Li0.90Ni0.10]NiO2 is identified at 600 °C even before the decomposition occurs. We also investigate the interplay of the reaction between LiNiO2 and CO2 with the decomposition at 700 °C. The changes in the Ni oxidation state and local Li environments are also monitored during the whole process.

Operando Elucidation of Electrocatalytic and Redox Mechanisms on a 2D Metal Organic Framework Catalyst for Efficient Electrosynthesis of Hydrogen Peroxide in Neutral Media.

The practical electrosynthesis of hydrogen peroxide (H2O2) is hindered by the lack of inexpensive and efficient catalysts for the two-electron oxygen reduction reaction (2e- ORR) in neutral electrolytes. Here, we show that Ni3HAB2 (HAB = hexaaminobenzene), a two-dimensional metal organic framework (MOF), is a selective and active 2e- ORR catalyst in buffered neutral electrolytes with a linker-based redox feature that dynamically affects the ORR behaviors. Rotating ring-disk electrode measurements reveal that Ni3HAB2 has high selectivity for 2e- ORR (>80% at 0.6 V vs RHE) but lower Faradaic efficiency due to this linker redox process. Operando X-ray absorption spectroscopy measurements reveal that under argon gas the charging of the organic linkers causes a dynamic Ni oxidation state, but in O2-saturated conditions, the electronic and physical structures of Ni3HAB2 change little and oxygen-containing species strongly adsorb at potentials more cathodic than the reduction potential of the organic linker (Eredox ∼ 0.3 V vs RHE). We hypothesize that a primary 2e- ORR mechanism occurs directly on the organic linkers (rather than the Ni) when E > Eredox, but when E < Eredox, H2O2 production can also occur through Ni-mediated linker discharge. By operating the bulk electrosynthesis at a low overpotential (0.4 V vs RHE), up to 662 ppm of H2O2 can be produced in a buffered neutral solution in an H-cell due to minimized strong adsorption of oxygenates. This work demonstrates the potential of conductive MOF catalysts for 2e- ORR and the importance of understanding catalytic active sites under electrochemical operation.

Adjusting electronic structure coupling of Fe–Ni2P (NiFeP-MOF) multilevel structure for ultra-activity and durable catalytic water oxidation

Efficient electrocatalyst for alkaline oxygen evolution reaction is the critical core to the wide application of metal-air energy storage and water electrolysis hydrogen energy. Therefore, appropriate design of highly active and stable non-noble metal oxygen evolution electrocatalyst with good electronic structure and multilevel structure is both a goal and a challenge. Here, we report a Fe–Ni2P electrocatalyst (NiFeP-MOF) with multilevel structure, which was obtained by anion exchange on the basis of Fe–Ni(OH)2 (NiFe-MOF) grown on nickel foam in situ by solvothermal method. As expected, Fe substitution regulates the Ni oxidation state in the NiFeP-MOF and realizes electronic structure coupling, showing a highly active and stable oxygen evolution reaction (OER) in alkaline electrolyte solution. Specifically, the NiFeP-MOF demonstrates an ultralow overpotentials (232 mV, 10 mA cm−2; 267 mV 100 mA cm−2), respectively, an extremely small Tafel slope (34 mV dec−1). Separately, the electrocatalyst shows an excellent cycle stability at 10 mA cm−2 for 12 h (43,200 s). More importantly, this work come up with an available policy for the preparation of excellent alkaline hydrolysis electrolysis catalysts and air cathodes with excellent performance.

C-H Bond Activation by a Mononuclear Nickel(IV)-Nitrate Complex.

The recent focus on developing high-valent non-oxo-metal complexes for late transition metals has proven to be an effective strategy to study the rich chemistry of these high-valent species while bypassing the synthetic challenges of obtaining the oxo-metal counterparts. In our continuing work of exploring late transition metal complexes of unusually high oxidation states, we have obtained in the present study a formal mononuclear Ni(IV)-nitrate complex (2) upon 1-e- oxidation of its Ni(III) derivatives (1-OH and 1-NO3). Characterization of these Ni complexes by combined spectroscopic and computational approaches enables deep understanding of their geometric and electronic structures, bonding interactions, and spectroscopic properties, showing that all of them are square planar complexes and exhibit strong π-covalency with the amido N-donors of the N3 ligand. Furthermore, results obtained from X-ray absorption spectroscopy and density functional theory calculations provide strong support for the assignment of the Ni(IV) oxidation state of complex 2, albeit with strong ligand-to-metal charge donation. Notably, 2 is able to oxidize hydrocarbons with C-H bond strength in the range of 76-92 kcal/mol, representing a rare example of high-valent late transition metal complexes capable of activating strong sp3 C-H bonds.