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At least 361 records · Page 20

Ammonia eurefstics: Electrolytes for liquid energy storage and conversion at room temperature and ambient pressure

Herein we report the transformation of gaseous ammonia to a liquid at room temperature and ambient pressure through mixing with simple solid ammonium salts. The resulting liquids, named eurefstics, are potentially advantageous for the storage and electrochemical conversion of ammonia and the realization of a green ammonia energy economy. Physical properties of these eurefstics, including the temperature-dependent composition and composition-dependent densities, are reported to glean initial insight into the formation and behavior of this intriguing liquid. Preliminary electrochemical investigations of the eurefstics were also performed. We have found that these eurefstics formed are conductive and can be used directly as electrolytes for ammonia electrolysis reactions to produce hydrogen on demand. Open-circuit potential measurements were also made to determine the formal potential of the hydrogen evolution and corresponding overpotentials. Finally, safety concerns of the eurefstics are discussed in comparison with other liquid phase energy carriers.

25 ENERGY STORAGE↗

Degrade-Repair Cycle of a Fuel-Forming Photoelectrode

Artificial leaves that produce fuels using sunlight hold promise for sustainably powering the planet, but they require advance- ments in energetic efficiency, cost effectiveness, and operational durability. Herein, we showcase the application of combined surface- sensitive spectroscopic techniques to durability studies that characterize structural changes accompanying functional degradation and go beyond just observing changes in function over time. Further, the photoelectrodes used in this work feature a polymeric surface coating functionalized with molecular complexes that catalyze the hydrogen evolution reaction. Using a polymeric layer to interface the light-harvesting component with catalytic sites enables reassembly of catalysts that detach during operation, establishing a degrade-repair cycle.

14 SOLAR ENERGY↗

Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS 2

We report the nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS 2 . Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS 2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS 2 under reaction conditions (H 2 atmosphere, 100–600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H 2 atmosphere). Conversely, the 6-fold Mo–Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS 2 is herein elucidated for applications in optoelectronics and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions

Polyoxometalates (POMs) featuring 7, 12, 18, or more redox-accessible transition metal ions are ubiquitous as selective catalysts, especially for oxidation reactions. The corresponding synthetic and catalytic chemistry of stable, discrete, capping-ligand-free polythiometalates (PTMs), which could be especially attractive for reduction reactions, is much less well developed. Among the challenges are the propensity of PTMs to agglomerate and the tendency for agglomeration to block reactant access of catalyst active sites. Nevertheless, the pervasive presence of transition metal sulfur clusters metalloenzymes or cofactors that catalyze reduction reactions and the justifiable proliferation of studies of two-dimensional (2D) metal-chalcogenides as reduction catalysts point to the promise of well-defined and controllable PTMs as reduction catalysts. Here, we report the fabrication of agglomeration-immune, reactant-accessible, capping-ligand-free Co II Mo 6 IV S 24 n– clusters as periodic arrays in a water-stable, hierarchically porous Zr-metal–organic framework (MOF; NU1K) by first installing a disk-like Anderson polyoxometalate, Co III Mo 6 VI O 24 m– , in size-matched micropores where the siting is established via difference electron density (DED) X-ray diffraction (XRD) experiments. Flowing H 2 S, while heating, reduces molybdenum(VI) ions to Mo(IV) and quantitatively replaces oxygen anions with sulfur anions (S 2– , HS – , S 2 2– ). DED maps show that MOF-templated POM-to-PTM conversion leaves clusters individually isolated in open-channel-connected micropores. Importantly, the structure of the immobilized cluster as determined, in part, by X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analysis, and pair distribution function (PDF) analysis of total X-ray scattering agrees well with the theoretically simulated structure. PTM@MOF displays both electrocatalytic and photocatalytic competency for hydrogen evolution. Nevertheless, the initially installed PTM appears to be a precatalyst, gaining competency only after the loss of ~3 to 6 sulfurs and exposure to hydride-forming metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Overview of Challenges and Strategies for Stabilizing Zinc Anodes in Aqueous Rechargeable Zn-Ion Batteries

Aqueous rechargeable zinc ion batteries (ZIBs) have been revived and are considered a promising candidate for scalable electrochemical energy storage systems due to their intrinsic safety, low cost, large abundance, mature recyclability, competitive electrochemical performance, and sustainability. However, the deployment of aqueous rechargeable ZIBs is still hampered by the poor electrochemical stability and reversibility of Zn anodes, which is a common, inherent issue for most metal-based anodes. This review presents a comprehensive and timely overview of the challenges and strategies of Zn anodes toward durable ZIBs. First, several challenges that significantly reduce the Coulombic efficiency and cycling stability of Zn anodes are briefly discussed including dendrite formation, hydrogen evolution, and corrosion. Then, the mitigation strategies are summarized in terms of modifying the electrode/electrolyte interfaces, designing electrode structures, and optimizing electrolytes and separators. Further, we comprehensively discuss the mechanisms behind these issues and improvement strategies with respect to the anodes, electrolytes, and separators. Lastly, we provide perspectives and critical analyses of remaining challenges, outlook, and future direction for accelerating the practical application of aqueous rechargeable ZIBs.

25 ENERGY STORAGE↗

Dislocation-Activated Low Platinum-Loaded PtCu Nanoparticles Welded onto the Substrate for Practical Acidic Hydrogen Generation

Although transition metal (M) alloying with platinum (Pt) is a promising approach to reduce the Pt dosage required in the hydrogen evolution reaction (HER), the catalytic activity and durability of PtM alloy are often unsatisfactory for acidic HER, especially at high currents, due to a reduced number of highly active sites (Pt) at the atomic level and challenges in stabilizing them to prevent detachment and aggregation. Herein, we report a robust functional structure integrated electrode (D-PtCu/CF) with abundant edge dislocations and very low platinum content (0.1 mg cm -2 ) to achieve high activity and stability in acidic HER within a proton exchange membrane water electrolysis cell (PEMWE). D-PtCu/CF exhibits high Pt mass activity (10.28 A mg Pt -1 ) and excellent operational stability (negligible decay after 200 h). X-ray absorption spectroscopy and in situ electrochemical experiments reveal that the lattice distortion caused by edge dislocations in PtCu mainly affects Pt atoms by compressing strain, reducing their ability to adsorb H. At the same time, Cu atoms are subjected to tensile strain, enhancing the bonding between Cu and H. Therefore, edge dislocations not only improve the intrinsic catalytic activity of Pt atoms but also increase the number of active sites (Cu) available for hydrogen adsorption, which synergistically accelerates the kinetics of the HER reaction. Finally, the PEMWE employing the D-PtCu/CF catalytic electrode can operate stably for 100 h at an industrial-level current density of 500 mA cm -2 with 1.63 V.

30 DIRECT ENERGY CONVERSION↗

Reconstructing Oxygen-Deficient Zirconia with Ruthenium Catalyst on Atomic-Scale Interfaces toward Hydrogen Production

Downsizing a catalyst nanoparticle (NP) to a single atom (SA) has proven to be highly effective in increasing catalytic activity and decreasing the amount of catalyst required for various electrochemical reactions. However, insufficient stability of the single-atom site catalysts (SACs) is still a significant challenge for their practical application. Here, SACs firmly bound to stable metal oxide NPs are proposed to dramatically increase the electrochemical activity and stability of SA-based catalysts for hydrogen evolution reaction (HER). Starting from a Ru-infiltrated, Zr-based metal-organic framework (MOF), the tetragonal zirconium oxide (ZrO 2-x ) NPs-embedded carbon matrix is fabricated as support through facile pyrolysis. Simultaneously, Ru SAs as active sites are well dispersed on the surface of ZrO 2-x NPs due to the generation of oxygen vacancies in the tetragonal ZrO 2-x . Finally, the Ru-ZrO 2-x SAC exhibits a 4–5 times higher mass activity than commercial Pt and Ru catalysts and superior durability due to strong metal-support interaction (SMSI) between Ru atoms and ZrO 2-x substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MX Anti-MXenes from Non-van der Waals Bulks for Electrochemical Applications: The Merit of Metallicity and Active Basal Plane

Two-dimensional transition-metal compounds (2DTMCs) are promising materials for electrochemical applications, but 2DTMCs with metallicity and active basal planes are rare. In this work, we proposed a simple and effective strategy to extract 2DTMCs from non-van der Waals bulk materials and established a material library of 79 2DTMCs, which we named as anti-MXenes since they are composed of one M atomic layer sandwiched by two X atomic layers. By means of density functional theory computations, 24 anti-MXenes were confirmed to be thermodynamically, dynamically, mechanically, and thermally stable. The metallicity and active basal plane endow these anti-MXenes with potential as excellent electrode materials, for example, as electrocatalysts for hydrogen evolution reactions (HER). Among the noble-metal free anti-MXenes with favorable H-binding, CuS can boost HER at the whole range of H coverages, while CoSi, FeB, CoB, and CoP show promise for HER at some specific H coverages. The active sites are the tetra-coordinating nonmetal atoms at the basal planes, thus rendering a very high density of active sites for these materials. CoB is also a promising anode material for lithium-ion batteries, showing low Li diffusion energy barriers, a very high capacity, and a suitable open circuit voltage. Overall, this work promotes the “computational exfoliation” of 2D materials from non-van der Waals bulks and exemplifies the applications of anti-MXenes in various electrochemical processes.

36 MATERIALS SCIENCE↗

Modulating Cu electrode microenvironments with MOF coatings: insights from molecular dynamics and electrochemical experiments of CO reduction

Metal-organic frameworks (MOFs) present a compelling strategy for tuning electrochemical interfaces by reshaping interfacial solvent structure. In this study, we examine how MOF coatings influence the microenvironment at copper electrodes during the CO electroreduction reaction (CORR) using a combined approach of molecular dynamics (MD) simulations and electrochemical experiments. Two MOFs, NU-901 and ZIF-8, are selected to explore the impact of pore size and channel hydrophobicity on electrochemical activity and interfacial concentration in acetonitrile (ACN) and dimethyl sulfoxide (DMSO) electrolytes. Electrochemical measurements reveal that MOF@Cu electrodes exhibit lower Faradaic efficiencies for CO hydrogenation products (ethylene and methane) compared to bare copper but have dramatic impacts on the interfacial microenvironment. NU-901, with its larger pores and strong interactions with DMSO, traps DMSO molecules and enhances CO coordination in DMSO but suppresses CORR selectivity in favor of the hydrogen evolution reaction (HER). ZIF-8, with smaller pores and hydrophobic channels, limits the interfacial water concentration, and, in ACN, promotes CO coordination. The simulations provide insights into how MOFs can act as physical modulators of reactant delivery and interfacial structure to control electrochemical microenvironments. This work highlights the value of molecular dynamics in uncovering how structural features of MOFs influence interfacial phenomena, even when catalytic performance is not directly improved.

Copper electrode microenvironments↗

Self-grown NiCuO x hybrids on a porous NiCuC substrate as an HER cathode in alkaline solution

Electrocatalysts converted directly from the substrates hold the key to achieve high catalytic activity and durability due to their high bonding strength, intimate electronic contact, and tunable phase composition. Herein, an electrically conductive porous NiCuC substrate was adopted to develop a multi-porous NiCuO x /NiCuC hydrogen evolution reaction (HER) catalyst using a one-step oxidation method in this research. The NiCuO x hybrids were characterized as three typical layers: an outer layer with NiCuO 2 solid solution phase, a partially oxidized intermediate layer, and an inner layer with limited stable oxygen content. Here, the NiCuO x /NiCuC possesses abundant Ni(II)–Cu(II) sites to accelerate the Volmer step via the electrostatic effect with OH – , numerous metallic NiCu sites to facilitate the H adsorption, and highly accessible channels to promote the Heyrovsky step during HER catalysis. As a result, high electrocatalytic performance was obtained with an overpotential of 116 mV at a current density of 10 mA cm –2 in 1.0 M potassium hydroxide, and a stable catalytic performance during the HER process for more than 24 h.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically active surface area controls HER activity for Fe x Ni 100–x films in alkaline electrolyte

We report the synthesis and electrocatalytic activity of Fe x Ni 100-x electrochemically deposited films were investigated. Films were evaluated for the hydrogen evolution reaction (HER) in alkaline media with respect to composition and electrochemically active surface area (ECSA). Results demonstrate that films of higher or equal Fe content had an ECSA tenfold greater than films with higher Ni. When normalized by geometric surface area, Fe 50 Ni 50 films required the lowest overpotential of -390 mV to reach a current density of -10 mA cm -2 . However, when normalized by the ECSA, intrinsic HER activity increases as Ni content increases. Tafel slope, ECSA, microscopy, and impedance spectroscopy analyses allow a decoupled analysis of surface area versus activity effects on overall measured HER activity. Furthermore, these analyses collectively demonstrate that the increase in electrocatalytic activity is attributed to the increase in ECSA and not to an enhancement in the intrinsic activity by Fe and Ni component interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying the Influence of Defects on Selectivity of Electrodes Encapsulated by Nanoscopic Silicon Oxide Overlayers

Encapsulation of electrocatalysts and photocatalysts with semipermeable nanoscopic oxide overlayers that exhibit selective transport properties is an attractive approach to achieve high redox selectivity. However, defects within the overlayers-such as pinholes, cracks, or particle inclusions-may facilitate local high rates of parasitic reactions by creating pathways for facile transport of undesired reactants to exposed active sites. Scanning electrochemical microscopy (SECM) is an attractive method to determine the influence of defects on macroscopic performance metrics thanks to its ability to measure the relative rates of competing electrochemical reactions with high spatial resolution over the electrode. Here, we report the use of SECM to determine the influence of overlayer defects on the selectivity of silicon oxide (SiOx) encapsulated platinum thin-film electrocatalysts operated under conditions where two competing reactions-the hydrogen evolution and Fe(III) reduction reactions-can occur. After an SECM methodology is described to determine spatially resolved selectivity, representative selectivity maps are correlated with the location of defects that are characterized by optical, electron, and atomic force microscopies. This analysis reveals that certain types of defects in the oxide overlayer are responsible for ∼60-90% of the partial current density toward the undesired Fe(III) reduction reaction. By correcting for defect contributions to Fe(III) reduction rates, true Fe(III) permeability values for the SiOxoverlayers were determined to be over an order of magnitude lower than permeabilities determined from analyses that ignore the presence of defects. Lastly, different types of defects were studied revealing that defect morphology can have varying influence on both redox selectivity and calculated permeability. This work highlights the need for spatially resolved measurements to evaluate the performance of oxide-encapsulated catalysts and understand their performance limits.

25 ENERGY STORAGE↗

Cobalt Metal–Cobalt Carbide Composite Microspheres for Water Reduction Electrocatalysis

Microspheres of cobalt metal–cobalt carbide (Co–Co x C, Co x C: Co 2 C and Co 3 C) composite with carbon shells were prepared via an OH – - and Cl – -assisted polyol method and explored for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic media. From our transmission electron microscopy observations, the outermost surfaces of the as-prepared Co–Co x C composites were primarily covered with Co 2 C crystallites. Our best performing electrocatalyst exhibited superior HER activity with an overpotential of 78 mV to reach a current density of -10 mA·cm –2 , a Tafel slope of 87.8 mV·dec –1 , and 1 h of electrode durability. We show that this excellent HER performance is primarily due to the superior intrinsic activity of Co 2 C, as well as the high electrical conductivity resulting from the inclusion of cobalt metal and the presence of graphitic carbon shells in and on the composite, respectively. Using both computational and experimental approaches, we determine here that the carbon-rich cobalt carbide (Co 2 C) phase is more favorable for the HER than the carbon-poor phase (Co 3 C).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring MoS 2 for Small-Molecule Electroreduction: The Role of Metal Doping and Heterostructures

The electrification of chemical transformations central to sustainable fuel production and waste valorization, such as overall water splitting (OWS), hydrogen evolution reaction (HER), and electrochemical reduction of CO 2 (CO 2 R), presents a powerful opportunity to advance carbon-neutral energy technologies. Transition metal dichalcogenides (TMDs), particularly MoS 2 , have emerged as promising electrocatalyst candidates, owing to their abundance, tunable active sites, and defect-rich structures. This review highlights recent progress in leveraging metal doping and heterostructure engineering of MoS 2 to enhance the electrocatalytic activity and selectivity. By compiling insights from experimental studies and density functional theory (DFT) predictions, we examine how defect creation, electronic structure modification, and interface design contribute to improved charge transport and catalytic efficiency. Particular emphasis is placed on rational design principles, synthetic strategies, and operando characterization methods that provide a pathway to understanding and optimizing MoS 2 -based materials. We also discuss the challenges of stability, mechanistic ambiguity, and scaling while outlining opportunities to bridge theory and experiment. Collectively, this review underscores how defect and heterostructure engineering of MoS 2 can accelerate the development of efficient, sustainable electrocatalysts for both fuel generation and waste-to-value generation.

CO2 reduction↗

Non-Equilibrium Synthesis of Highly Active Nanostructured, Oxygen-Incorporated Amorphous Molybdenum Sulfide HER Electrocatalyst

Molybdenum sulfide emerged as promising hydrogen evolution reaction (HER) electrocatalyst thanks to its high intrinsic activity, however its limited active sites exposure and low conductivity hamper its performance. To address these drawbacks, the non-equilibrium nature of pulsed laser deposition (PLD) is exploited to synthesize self-supported hierarchical nanoarchitectures by gas phase nucleation and sequential attachment of defective molybdenum sulfide clusters. Furthermore, the physics of the process are studied by in situ diagnostics and correlated to the properties of the resulting electrocatalyst. The as-synthesized architectures have a disordered nanocrystalline structure, with nanodomains of bent, defective S-Mo-S layers embedded in an amorphous matrix, with excess sulfur and segregated molybdenum particles. Oxygen incorporation in this structure fosters the creation of amorphous oxide/oxysulfide nanophases with high electrical conductivity, enabling fast electron transfer to the active sites. The combined effect of the nanocrystalline pristine structure and the surface oxidation enhances the performance leading to small overpotentials, very fast kinetics (35.1 mV dec -1 Tafel slope) and remarkable long-term stability for continuous operation up to -1 A cm -2 . This work shows possible new avenues in catalytic design arising from a non-equilibrium technique as PLD and the importance of structural and chemical control to improve the HER performance of MoS-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving and Understanding the Hydrogen Evolving Activity of a Cobalt Dithiolene Metal–Organic Framework

Despite the promising previous reports on the development of electrocatalytic dithiolene-based metal–organic frameworks (MOFs) for the hydrogen evolution reaction (HER), these materials often display poor reproducibility of the HER performance because of their poor bulk properties upon integration with electrode materials. In this work, we demonstrate an in-depth investigation of the electrocatalytic HER activity of a cobalt 2,3,6,7,10,11-triphenylenehexathiolate (CoTHT) MOF. To enhance the durability and charge transport properties of the constructed CoTHT/electrode architecture, CoTHT is deposited as an ink composite (1) composed of Nafion and carbon black. We leverage here the well-established use of catalyst inks in the literature to increase adhesion of the catalyst to the electrode surface and to improve the overall electrical conductivity of the integrated catalyst/electrode. The utilization of the composite 1 leads to a significant improvement in the overpotential (η) to reach a current density of 10 mA/cm 2 (η = 143 mV) compared to prior reports, resulting in the most active MOF-based electrocatalyst for the HER that contains only earth-abundant elements. Extensive density functional theory (DFT) calculations were applied to understand the structure of CoTHT and the mechanistic pathways of the HER. The computational results suggest that an AB stacking geometry is energetically favorable, where one layer is slipped by 1.6 Å relative to the neighboring one along the a and b vectors. Additionally, the DFT calculations indicate that the catalytic cycle likely involves a Volmer discharge step to generate a cobalt hydride, followed by a Heyrovsky step to form a cobalt–H 2 intermediate, and finally the dissociation of H 2 .

DFT calculations↗

Seawater alkalization via an energy-efficient electrochemical process for CO 2 capture

Electrochemical pH-swing strategies offer a promising avenue for cost-effective and energy-efficient carbon dioxide (CO 2 ) capture, surpassing the traditional thermally activated processes and humidity-sensitive techniques. The concept of elevating seawater’s alkalinity for scalable CO 2 capture without introducing additional chemical as reactant is particularly intriguing due to its minimal environmental impact. However, current commercial plants like chlor-alkali process or water electrolysis demand high thermodynamic voltages of 2.2 V and 1.23 V, respectively, for the production of sodium hydroxide (NaOH) from seawater. These high voltages are attributed to the asymmetric electrochemical reactions, where two completely different reactions take place at the anode and cathode. Here, we developed a symmetric electrochemical system for seawater alkalization based on a highly reversible and identical reaction taking place at the anode and cathode. We utilize hydrogen evolution reaction at the cathode, where the generated hydrogen is looped to the anode for hydrogen oxidation reaction. Theoretical calculations indicate an impressively low energy requirement ranging from 0.07 to 0.53 kWh/kg NaOH for established pH differences of 1.7 to 13.4. Experimentally, we achieved the alkalization with an energy consumption of 0.63 kWh/kg NaOH, which is only 38% of the theoretical energy requirements of the chlor-alkali process (1.64 kWh/kg NaOH). Further tests demonstrated the system’s potential of enduring high current densities (~20 mA/cm 2 ) and operating stability over an extended period (>110 h), showing its potential for future applications. Notably, the CO 2 adsorption tests performed with alkalized seawater exhibited remarkably improved CO 2 capture dictated by the production of hydroxide compared to the pristine seawater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗