Solid-state Nuclear Magnetic Resonance Measurements Research Articles

Elucidating Consequences of Selenium Crystallinity on Its Electrochemical Reduction in Aluminum-Selenium Batteries.

Selenium (Se) is an attractive positive electrode material for rechargeable aluminum (Al) batteries due to its high theoretical capacity of 2037 mA h g-1 and its higher electronic conductivity compared to sulfur. Selenium can undergo a series of electrochemical reactions between Se(-II) and Se(IV), resulting in a six-electron capacity per Se atom. However, existing Al-Se battery literature is inconsistent regarding the different electrochemical reactions possible, while the conditions enabling the electrochemical reduction of Se to Al2Se3 are not well understood. Here, we demonstrate that this electrochemical reduction is achievable using amorphous selenium but is suppressed for crystalline selenium. We further show that the electrochemical oxidation of Se to SeCl4, which occurs at higher potentials, reduces the long-range order of crystalline Se and enables its discharge to Al2Se3. Solid-state 77Se nuclear magnetic resonance (NMR) measurements further establish that the local Se helical structures are maintained upon the loss of crystallinity.

Elucidating the Role of Electrochemically Formed LiF in Discharge and Aging of Li-CFx Batteries.

Fifty years after its introduction, the lithium-carbon monofluoride (Li-CFx) battery still has the highest cell-level specific energy demonstrated in a practical cell format. However, few studies have analyzed how the main electrochemical discharge product, LiF, evolves during the discharge and cell rest periods. To fill this gap in understanding, we investigated molecular-level and interfacial changes in CFx electrodes upon the discharge and aging of Li-CFx cells, revealing the role of LiF beyond that of a simple discharge product. We reveal that electrochemically formed LiF deposits on the surface of the CFx electrode and subsequently partially disperses into the electrolyte to form a colloidal suspension during cell aging, as determined from galvanostatic electrochemical impedance spectroscopy (EIS), solid-state 19F nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and operando optical light microscopy measurements. Electrochemical LiF formation and LiF dispersion into the electrolyte are distinct competing rate processes that each affect the cell impedance differently. Using knowledge of LiF dispersion and saturation, an in-line EIS method was developed to compute the depth of discharge of CFx cells beyond coulomb counting. Solid-state 19F NMR measurements quantitatively revealed how LiF and CF moieties evolved with discharge. Covalent CF bonds react first, followed by a combination of covalent and ionic CF bonds. Quantitively correlating NMR and electrochemical measurements reveals not only how LiF formation affects cell impedance but also that CF bonds with the most ionic character remain unreacted, which limits realization of the full theoretical specific capacity of the CFx electrode. The results reveal new insights into the electrochemical discharge mechanism of Li-CFx cells and the unique role of LiF in cell discharge and aging, which suggest pretreatment strategies and methods to improve and measure the performance of Li-CFx batteries.

Water-Enhanced Direct Air Capture of Carbon Dioxide in Metal-Organic Frameworks.

We have developed two series of amine-functionalized zirconium (Zr) metal-organic framework-808 (MOF-808), which were produced by postsynthetic modifications to have either amino acids coordinated to Zr ions (MOF-808-AAs) or polyamines covalently bound to the chloro-functionalized structure (MOF-808-PAs). These MOF variants were comprehensively characterized by liquid-state 1H nuclear magnetic resonance (NMR) measurements and potentiometric acid-base titration to determine the amounts of amines, energy-dispersive X-ray spectroscopy to assess the extent of covalent substitution by polyamines, powder X-ray diffraction analysis to verify the maintenance of the MOF crystallinity and structure after postsynthetic modifications, nitrogen sorption isotherm measurements to confirm retention of the porosity, and water sorption isotherm measurements to find the water uptake in the pores of each member of the series. Evaluation and testing of these compounds in direct air capture (DAC) of CO2 showed improved CO2 capture performance for the functionalized forms, especially under humid conditions: In dry conditions, the l-lysine- and tris(3-aminopropyl)amine-functionalized variants, termed as MOF-808-Lys and MOF-808-TAPA, exhibited the highest CO2 uptakes at 400 ppm, measuring 0.612 and 0.498 mmol g-1, and further capacity enhancement was achieved by introducing 50% relative humidity, resulting in remarkable uptakes of 1.205 and 0.872 mmol g-1 corresponding to 97 and 75% increase compared to the dry uptakes, respectively. The mechanism underlying the enhanced uptake efficiency was revealed by 13C solid-state NMR and temperature-programmed desorption measurements, indicating the formation of bicarbonate species, and therefore a stoichiometry of 1:1 CO2 to each amine site.

Atomistic, macromolecular model of the Populus secondary cell wall informed by solid-state NMR.

Plant secondary cell walls (SCWs) are composed of a heterogeneous interplay of three major biopolymers: cellulose, hemicelluloses, and lignin. Details regarding specific intermolecular interactions and higher-order architecture of the SCW superstructure remain ambiguous. Here, we use solid-state nuclear magnetic resonance (ssNMR) measurements to infer refined details about the structural configuration, intermolecular interactions, and relative proximity of all three major biopolymers within air-dried Populus wood. To enhance the utility of these findings and enable evaluation of hypotheses in a physics-based environment in silico, the NMR observables are articulated into an atomistic, macromolecular model for biopolymer assemblies within the plant SCW. Through molecular dynamics simulation, we quantitatively evaluate several variations of atomistic models to determine structural details that are corroborated by ssNMR measurements.

Achieving narrow bandwidth and high stimulated cross-section in Nd3+-doped LiCaB glasses for near infra-red laser amplifiers

The aim of this research is to examine the effects of Nd3+ ions on the spectroscopic characteristics of different concentrations of lithium-calcium-borate glasses and improve the emission cross section alongside bandwidth. The prepared glasses were produced with the melt-quenching technique and were thoroughly analyzed to determine their usefulness as laser amplifiers. Various studies were conducted, including X-ray diffraction (XRD), solid-state nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), absorption and emission measurements, and time decay curve measurements. The structural analysis using XRD and NMR techniques revealed that the glasses were amorphous and that non-bridging oxygen was present. Moreover, it was discovered that the glass-forming tendency and glass stability of these glasses improved with the concentration of Nd3+ ions. The glasses' absorption spectra display 10 transition states in UV and visible regions. Among all the prepared glasses, the lithium-calcium-borate glass doped with 0.5 mol % Nd3+ ions stand out with a stimulated emission cross-section value of 3.40 × 10−20 cm2 and a narrow bandwidth of 33 nm, making it an ideal lasing amplifier medium due to the 4F3/2 → 4I11/2 (1060 nm) transition. Theoretical Judd-Ofelt calculations were conducted to evaluate various parameters, including oscillatory strength, radiative parameters, radiative lifetime, gain bandwidth, figure-of-merit, and saturation current, for all transitions in the near-infrared region, to support the experimental investigations and offer a detailed discussion of these parameters.

High dielectric filler for all-solid-state lithium metal battery

Lithium metal with its high theoretical capacity and low negative potential is considered one of the most important candidates to raise the energy density of all-solid-state batteries. However, lithium filament growth and its induced solid electrolyte decomposition pose severe challenges to realize a long cycle life. Here, dendrite growth in solid-state Li metal batteries is alleviated by introducing a high dielectric material, barium titanate, as a filler that removes the electric field gradients that catalyze dendrite formation. In symmetrical Li-metal cells, this results in a very small over-potential of only 48 mV at a relatively high current density of 1 mA cm−2, when cycling a capacity of 2 mA h cm−2 during 1700 h. The high dielectric filler improves the Coulombic efficiency and cycle life of full cells and suppresses electrolyte decomposition as indicated by solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) measurements. This indicates that the high dielectric filler can suppress dendrite formation, thereby reducing solid electrolyte decomposition reactions, resulting in the observed low overpotentials and improved cycling efficiency.

The temperature increase in carbon materials during magic-angle spinning solid-state nuclear magnetic resonance measurements

The temperature increase in carbon materials during magic-angle spinning solid-state nuclear magnetic resonance measurements

Charting the solid-state NMR signals of polysaccharides: A database-driven roadmap.

Solid-state nuclear magnetic resonance (ssNMR) measurements of intact cell walls and cellular samples often generate spectra that are difficult to interpret due to the presence of many coexisting glycans and the structural polymorphism observed in native conditions. To overcome this analytical challenge, we present a statistical approach for analyzing carbohydrate signals using high-resolution ssNMR data indexed in a carbohydrate database. We generate simulated spectra to demonstrate the chemical shift dispersion and compare this with experimental data to facilitate the identification of important fungal and plant polysaccharides, such as chitin and glucans in fungi and cellulose, hemicellulose, and pectic polymers in plants. We also demonstrate that chemically distinct carbohydrates from different organisms may produce almost identical signals, highlighting the need for high-resolution spectra and validation of resonance assignments. Our study provides a means to differentiate the characteristic signals of major carbohydrates and allows us to summarize currently undetected polysaccharides in plants and fungi, which may inspire future investigations.

Development of High-Temperature Superconducting Coil for Solid-State NMR Experiments

Abstract A high-temperature superconducting (HTS) coil, in which YBa2Cu3O7-δ is vapor-deposited on the surface of a sapphire plane, has been developed to increase signal-to-noise ratios (SNR) in solid-state nuclear magnetic resonance (NMR) measurements. The Q-factor of the NMR probe is found to be 16,125 at the resonant frequency of 38.525 MHz. A single sharp signal, full width at half maximum of 20 ppm, can be detected by the HTS coil in a stationary solid-state 79Br NMR spectrum of a polycrystalline potassium bromide at the temperature of 9 K. Compared with the results for an isomorphic copper coil, an improvement of a factor of 6.6 is obtained for SNR, indicating that accumulation time of NMR experiments can be reduced to 1/44.

On the Discrepancy between Local and Average Structure in the Fast Na+ Ionic Conductor Na2.9Sb0.9W0.1S4

Aliovalent substitution is a common strategy to improve the ionic conductivity of solid electrolytes for solid-state batteries. The substitution of SbS43- by WS42- in Na2.9Sb0.9W0.1S4 leads to a very high ionic conductivity of 41 mS cm-1 at room temperature. While pristine Na3SbS4 crystallizes in a tetragonal structure, the substituted Na2.9Sb0.9W0.1S4 crystallizes in a cubic phase at room temperature based on its X-ray diffractogram. Here, we show by performing pair distribution function analyses and static single-pulse 121Sb NMR experiments that the short-range order of Na2.9Sb0.9W0.1S4 remains tetragonal despite the change in the Bragg diffraction pattern. Temperature-dependent Raman spectroscopy revealed that changed lattice dynamics due to the increased disorder in the Na+ substructure leads to dynamic sampling causing the discrepancy in local and average structure. While showing no differences in the local structure, compared to pristine Na3SbS4, quasi-elastic neutron scattering and solid-state 23Na nuclear magnetic resonance measurements revealed drastically improved Na+ diffusivity and decreased activation energies for Na2.9Sb0.9W0.1S4. The obtained diffusion coefficients are in very good agreement with theoretical values and long-range transport measured by impedance spectroscopy. This work demonstrates the importance of studying the local structure of ionic conductors to fully understand their transport mechanisms, a prerequisite for the development of faster ionic conductors.

Chemical shift tensors as probes of chalcogen bonds: solid-state NMR study of telluradiazole-XCN− (X = O, S, Se) salt cocrystals

We report experimental 125Te magic-angle spinning solid-state nuclear magnetic resonance (MAS NMR) measurements of the tellurium chemical shift (CS) tensors in three [K(18-crown-6)]+ 3,4-dicyano-1,2,5-telluradiazole-XCN− (X = O, S, Se) salt cocrystals featuring chalcogen bonds. These data are compared to those for pure 3,4-dicyano-1,2,5-telluradiazole (1). A reduction in the span of the 125Te CS tensor is consistently noted in the salt cocrystals compared to pure 1. Isotopically 15N-labelled [K(18-crown-6)]+[1-OC15N]−, which features a chalcogen bond between Te and the cyanate nitrogen atom, is synthesized using KOC15N, and the nitrogen CS tensors are measured for both samples via 15N slow MAS NMR spectroscopy. Possible dynamic disorder of the cyanate ions in KOCN is ruled out. Two crystallographically distinct nitrogen sites are resolved for the salt cocrystal. Upon formation of [K(18-crown-6)]+[1-OC15N]−, the 15N isotropic CS and CS tensor span both decrease relative to the values for pure KOC15N, and the axial symmetry of this tensor is lost. These findings are supplemented with a series of density functional theory calculations of magnetic shielding tensors using cluster models or periodic boundary conditions. Inclusion of spin–orbit relativistic effects in the calculation of tellurium shielding tensors is particularly important in achieving agreement with experiment.

Tunable Solid Acid Catalyst Thin Films Prepared by Atomic Layer Deposition.

Solid acid catalysts, including zeolites and amorphous silica-aluminas (ASAs), are industrially important materials widely used in the fuel and petrochemical industries. The versatility of zeolites is due to the Brønsted acidity of the bridging hydroxyl and shape selectivity that can be tailored during and after synthesis. This is in contrast to amorphous silica-alumina, where tailoring acidity is a major challenge as the Brønsted acid structure in ASA is still debated. In both cases, however, the pore size and acidity cannot be tuned independently, and this is particularly limiting in the application of biomass conversion, where zeolite pores are too small for the molecules of interest. Herein, we present a method using atomic layer deposition (ALD) to prepare thin films of solid acid materials where the ratio of Brønsted to Lewis acid sites can be tuned precisely. This capability, combined with the sub-nm pore size control afforded by ALD yields a powerful and flexible method for synthesizing solid acid catalysts inside virtually any mesoporous host. We demonstrate the utility of these materials in two acid-catalyzed reactions relevant to biomass conversion: (1) Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction and dehydration of fructose and (2) cascade reaction of glucose to 5-hydroxymethylfurfural. Finally, we propose a plausible structure for the Brønsted acid sites in our materials based on infrared spectroscopy and solid-state nuclear magnetic resonance measurements and density functional theory calculations and argue that this same structure might apply to conventional ASAs as well.

Solid-state 1H and 13C NMR studies of novel ionic rotator-crystals of [NEt x Me(3−x)R][BEt4] (R = Pr, Bu. x = 1, 2)

Abstract Four new ionic rotator-crystals of [NEt x Me(3−x)R][BEt4] (R = Pr, Bu; x = 1, 2) were observed. Rotator crystals (two-dimensional plastic crystals) are mesophases between solid and isotropic liquid phases. Solid-state 1H and 13C nuclear magnetic resonance (NMR) measurements revealed that the ellipsoidal cations of [NEt x Me(3−x)R]+ undergo uniaxial rotation about their N–R axis and libration motion of the axis, and the anions perform isotropic reorientations in the highest-temperature solid-phase (rotator phase). Differential scanning calorimetry (DSC) measurements showed small entropy changes of 8–11 J K−1 mol−1 at the melting point of the compounds. These results suggest that the cations and anions have large degrees of freedom of motion in the rotator phase. The diffraction patterns of X-ray diffraction (XRD) could be indexed to the trigonal structure (space group of P31c). Compared with the reported data for [NEt x Me(3−x)Pr][BEt3Me] (x = 1, 2) compounds, which also have rotator-crystal phases and transform to a plastic crystalline phase, a model that explains why the cations of [BEt4] salts hardly perform isotropic reorientation in the solid phases was proposed.

Preparation and characterization of fluorine-substituted LiFeBO3 with carbon coating to enhance electrochemical performance and stability as a cathode material for Li-ion batteries

The fluorine-substituted LiFeBO3 with carbon coating (LFeBF/C) has been successfully demonstrated via a solid-state reaction to enhance its electrochemical properties and stability in air. Transmission electron microscopy characterization reveals that the primary LFeBF particles are fully covered by a thin layer of amorphous carbon. The formation of vonsenite-type LFeBF/C and the distribution of Li ions into its octahedral sites due to the fluorine substitution are confirmed using X-ray diffraction and solid-state nuclear magnetic resonance measurements, respectively. The stability of the LFeBF/C in air is promoted by the carbon layer. After two months of open-air storage, no significant changes in X-ray diffraction patterns can be observed. The synergistic effects of fluorine substitution and carbon coating enhance the overall electrochemical performance of the LFeBF/C as achieving a superior initial discharge capacity of 367.0 mAh g−1 at the rate of 0.05C and 231.7 mAh g−1 at 1.0C. In addition, the cyclic stability of the LFeBF/C is improved, reaching 197.5 mAh g−1 at the rate of 1.0C after 50 cycles, which corresponds to a retention of 85% of its initial capacity.

High dielectric barium titanate porous scaffold for efficient Li metal cycling in anode-free cells

Li metal batteries are being intensively investigated as a means to achieve higher energy density when compared with standard Li-ion batteries. However, the formation of dendritic and mossy Li metal microstructures at the negative electrode during stripping/plating cycles causes electrolyte decomposition and the formation of electronically disconnected Li metal particles. Here we investigate the use of a Cu current collector coated with a high dielectric BaTiO3 porous scaffold to suppress the electrical field gradients that cause morphological inhomogeneities during Li metal stripping/plating. Applying operando solid-state nuclear magnetic resonance measurements, we demonstrate that the high dielectric BaTiO3 porous scaffold promotes dense Li deposition, improves the average plating/stripping efficiency and extends the cycling life of the cell compared to both bare Cu and to a low dielectric scaffold material (i.e., Al2O3). We report electrochemical tests in full anode-free coin cells using a LiNi0.8Co0.1Mn0.1O2-based positive electrode and a LiPF6-based electrolyte to demonstrate the cycling efficiency of the BaTiO3-coated Cu electrode.

Enhancing the structure and properties of fluoro-sulfo-phosphate laser glass via Zn(PO3)2 incorporation

Multi-anion fluoro-sulfo-phosphate (FSP) glass with the compositions of KPO3–Zn(PO3)2–AlF3–Na2SO4 (labeled as KZFSP) was designed. Effects of Zn(PO3)2 incorporation on glass structure and properties were investigated through Raman and Fourier transform infrared (FTIR) spectrometers, solid-state nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC) measurements, etc. Structure analyses reveal that adding Zn(PO3)2 raises the polymerization degree of skeleton structure and enhances the bonding strength between cations and anions, which improves the physicochemical properties. Optimized KZFSP glass shows excellent anti-crystallization ability (ΔT >224 °C), mechanical properties and chemical durability compared with KPO3-based FSP glass. Nd3+-doped KZFSP glass exhibits a relatively large figure of merit (~1.02 × 10–23 cm2•s) and low saturation intensity (~1.84 × 108 W•m–2), which is a promising material for high-performance single-frequency or high-repetition-frequency lasers.

Solid-state nuclear magnetic resonance of spin-9/2 nuclei 115 In and 209 Bi in functional inorganic complex oxides.

Indium and bismuth are technologically important elements, in particular as oxides for optoelectronic applications. 115 In and 209 Bi are both I = 9/2 nuclei with high natural abundances and moderately high frequencies but large nuclear electric quadrupole moments. Leveraging the quadrupolar interaction as a measure of local symmetry and polyhedral distortions for these nuclei could provide powerful insights on a range of applied materials. However, the absence of reported nuclear magnetic resonance (NMR) parameters on these nuclei, particularly in oxides, hinders their use by the broader materials community. In this contribution, solid-state 115 In and 209 Bi NMR of three recently discovered quaternary bismuth or indium oxides are reported, supported by density functional theory calculations, numerical simulations, diffraction and additional multinuclear (27 Al, 69,71 Ga, and 121 Sb) solid-state NMR measurements. The compounds LiIn2 SbO6 , BiAlTeO6 , and BiGaTeO6 are measured without special equipment at 9.4 T, demonstrating that wideline techniques such as the QCPMG pulse sequence and frequency-stepped acquisition can enable straightforward extraction of quadrupolar tensor information in I = 9/2 115 In and 209 Bi even in sites with large quadrupolar coupling constants. Relationships are described between the NMR observables and local site symmetry. These are amongst the first reports of the NMR parameters of 115 In, 121 Sb, and 209 Bi in oxides.

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO2 to Epoxides under Mild Conditions.

We have devised a straightforward tandem postsynthetic modification strategy for Zr-based metal–organic framework (MOF) materials, which resulted in a series of well-defined 2-in-1 heterogeneous catalysts, cat1–cat8, exhibiting high catalytic activity in the synthesis of cyclic carbonates under solvent-free and co-catalyst-free conditions. The materials feature precisely located co-catalyst moieties decorating the metal nodes throughout the bulk of the MOF and yield cyclic carbonates with up to 99% efficiency at room temperature. We use diffuse reflectance infrared Fourier transform (DRIFT) and solid-state nuclear magnetic resonance (NMR) measurements to elucidate the role of each component in this model catalytic reaction. Establishing a method to precisely control the co-catalyst loading allowed us to observe the cooperativity between Lewis acid sites and the co-catalyst in the 2-in-1 heterogeneous system.

Elucidating Reversible Electrochemical Anionic Redox in Intercalation Electrodes for Rechargeable Multivalent-Ion Batteries

Battery electrodes that enable electrochemical intercalation of multivalent ions result in multiple electron transfers per ion, respectively, yielding significant enhancements in electric charge storage capacity. When multivalent cathodes are paired with their corresponding metal anodes, potentially transformative gains in energy density are possible. However, few positive electrode materials exist that intercalate multivalent ions, in part due to the slow solid-state diffusion of highly charged multivalent ions. The chevrel phases Mo6X8, where X is a chalcogen atom (e.g., S or Se) are among the few materials known to reversibly and electrochemically intercalate both divalent (e.g. Mg2+, Zn 2+, etc.) and trivalent (Al3+) ions. Thus, understanding the ion intercalation and electron charge transfer mechanisms within these unique compounds may provide insights into the molecular-level design of new intercalation electrodes for rechargeable multivalent ion batteries.Here, we couple electrochemical and solid-state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) measurements to reveal the concurrent aluminum-ion intercalation and electron charge transfer mechanisms in chevrel electrodes Mo6S8 and Mo6Se8 up from the molecular level. Solid-state 27Al single-pulse MAS NMR measurements were performed on the thio-chevrel Mo6S8 electrodes at different states-of-charge to observe changes in the environments and to quantify the local populations of aluminum ions within the host crystal structure, revealing both intercalated ions and additional aluminum species associated with surface layers and/or decomposition products. Al-Mo6Se8 batteries were made for the first time and their electrochemical properties were compared to the thio-chevrel Mo6S8. Solid-state 77Se and 95Mo MAS NMR measurements on the seleno-chevrel Mo6Se8 at charged and discharged states revealed that electrons are transferred preferentially to the anionic chalcogen framework upon aluminum ion intercalation, as opposed to the transition metals (Mo). Anionic redox was further confirmed by density functional theory (DFT) calculations and X-ray absorption near-edge structure (XANES) measurements. Lastly, we generalize the results to other ion valencies, demonstrating reversible electrochemical anionic redox in the Chevrel phase upon divalent Zn2+ cations in aqueous Zn batteries.Overall, for the first time, we demonstrate reversible electrochemical anionic redox as a charge storage mechanism for rechargeable batteries, which preserves the crystalline framework structure and does not involve the breaking and forming of chemical bonds. This charge storage mechanism is fundamentally different than that observed for lithium-ion intercalation into transition metal oxides, where the electrons are stored within the d-orbitals of the transition metal. The results suggest materials design principles aimed at designing multivalent-ion intercalation electrodes with improved electrochemical properties. Figure 1

Electrochemical Control and Understanding of the Electronic and Optical Properties of ZnO Formed in Rechargeable Zn-Alkaline Batteries

Rechargeable alkaline batteries using zinc metal (Zn) electrodes are of significant interest for next-generation energy storage because of their high energy density, low cost, environmental friendliness, and inherent safety. Rechargeable Zn-alkaline batteries, however, have not been widely commercialized in part due to the low cyclability of Zn electrodes. At high depths of discharge, zinc oxide (ZnO) discharge product accumulates in the electrode, passivating the zinc-electrolyte interface and ultimately leading to cell failure. While the ZnO discharge product has been studied for decades, there is no general consensus on its local structure, composition, and electrochemical properties, nor on how these properties are affected by the electrode potential or cycling conditions.In this work, we used in operando analytical techniques including X-Ray diffraction (XRD), confocal Raman spectroscopy, electrochemical impedance spectroscopy (EIS), and ultraviolet-visible (UV-vis) spectroscopy to demonstrate that the discharge product is proton-doped ZnO with oxygen vacancies, and that the electrical conductivity, band gap, and color vary systematically as a function of electrode potential. To investigate local hydrogen and zinc environments within the ZnO discharge product, we performed ex situ solid-state 1H, 2H, and 67Zn magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. Solid-state 1H and 2H NMR measurements establish that hydrogen environments change as a function of potential, while solid-state 67Zn NMR spectra indicate that the local zinc environments are distorted compared to ZnO generated via conventional routes. We also performed 2D 1H-1H exchange (EXSY) NMR measurements to investigate proton mobility between defect environments and acquired 1D 1H-1H dipolar-mediated double quantum-filtered MAS NMR spectra to establish through-space molecular-level proximities between proton sites. This work provides insights into the dynamics of zinc electrodes in alkaline environments, as well as how to electrochemically control the defect structures and electronic and optical properties of ZnO in alkaline media, which are expected to aid the development of next-generation Zn alkaline batteries and electronic devices utilizing ZnO.