Search NASA⌕ Search

SEARCH · Search NASA

Results for “catalyst efficiency”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,765 records · Page 98

Water Splitting by Thin Film Metal-Oxo Catalysts

The dropping price of silicon photovoltaics in the United States is causing load defection to solar supply at an accelerated pace. This conversion to solar and, more generally, other renewable energy sources has accordingly turned the energy research focus from generation to one of storage. Truly disruptive improvements in energy storage technologies are limited by energy density. This limitation, however, does not apply to fuels, which possess the energy density needed for large-scale energy storage. The first step of the basic science needed to drive such historic restructuring of the U.S. energy infrastructure begins with the solar-driven generation of hydrogen and oxygen from water. The solar-produced hydrogen may then be combined with carbon dioxide to deliver any number of fuels. Obviously, light does not directly act on water to engender its splitting into its elemental components. Hence, catalysts are needed to drive the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Of these two reactions, the four-electron, four-proton oxidation of OER is the more kinetically challenging reaction, and therefore the development of energy efficient solar fuels processes demands that OER be accomplished at a minimal overpotential. The research completed in this program developed catalysts that drive OER and at the same time meet the important criteria of (1) using non-critical materials that (2) are easy to assemble and (3) accomplish OER under simple conditions. Research was designed to uncover the chemical principles that underlie the self-assembly of metal oxide oxygen evolving catalysts (M-OEC) from the metals of M = Mn, Co, and Ni. For example, a dogma of heterogeneous catalysis of any sort is that “edges” matter in promoting catalytic transformations. We provided a rationale for such dogma by showing that the OER in Co-OEC occurred at a dimensionally reduced dicobalt edge site. Edge site reactivity was clearly revealed analyzing 18O labeled OER with differential electrochemical mass spectrometry (DEMS) of Co-OEC. The OER mechanism of M-OECs was examined with complementary studies of model dicobalt compounds that captured the critical steps of the OER reaction. Additionally, the role of activating M-OECS with metal ion dopants was defined by developing structure–function relationships, guided by the principles of inorganic chemistry. We found that the M(IV) oxidation state in oxidic OER frameworks was correlated to the presence of the dopant metal, as assessed by coulometric titration and ICP-MS analysis. To investigate why greater M(IV) valence is beneficial to greater catalytic OER activity, we probed the influence of formal M valence on the electronic structure of oxygen ions in M-OECs by undertaking O and Ni K-edge spectroscopy, which revealed greater M-O covalency and hence M-oxyl radical character with M(IV) formation. Such oxyl radical character is consistent with increasing evidence for the role of oxygen radicals in O–O bond formation by a proton-coupled electron transfer mechanism involving water, to generate a hydroperoxide intermediate from which oxygen is generate. In accomplishing this science, the DOE program leveraged its expertise in spectroscopy and structural methods, inorganic and materials synthesis, and electrochemical characterization. The knowledge garnered from this proposed program enables the design of next generation catalysts with improved OER kinetics that operate over a wide range of conditions and environments.

25 ENERGY STORAGE↗

Understanding Inlet Concentration Effects on the Electrocatalytic Conversion of CO 2 to Formic Acid in Gas-Fed Electrolyzers

The electrochemical CO 2 reduction reaction (CO2RR) to produce value-added products remains a developing technology for utilizing waste CO 2 streams. Most device-level CO2RR studies use pure CO 2 gas feeds; however, the effect of dilute CO 2 on the electrolyzer performance is an important consideration for large-scale electrolyzer operation, single-pass conversion, and real-world CO 2 source utilization. This work investigates the effect that the CO 2 concentration has on the performance of formic acid (HCOOH) producing tin oxide (SnO 2 ) and bismuth oxide (Bi 2 O 3 ) catalysts in an electrolyzer device setting. Surprisingly, SnO2 demonstrated an approximately 20% increase in HCOOH selectivity (Faradaic efficiency) when the CO 2 concentration decreased from 100 to 20%. In contrast, Bi 2 O 3 consistently demonstrated high selectivity toward HCOOH across the same CO 2 concentration range. The effects of the CO 2 concentration on selectivity were further investigated with half-cell experiments and in situ Raman spectroscopy, which revealed dynamic changes in the cathodic overpotential and chemical state of the catalyst that depended on the CO 2 concentration. Density functional theory calculations showed how changes in the surface oxidation state of Sn, varying from fully oxidized SnO 2 to metallic Sn(0), affect the thermodynamic barriers of the three main observed products: HCOOH, CO, and H 2 . Our results indicate that dilute CO 2 concentrations required larger cathodic overpotentials to sustain a fixed current density, which, in turn, pushed the Sn-based catalyst toward a more reduced surface that was favorable to HCOOH formation. On the other hand, the Bi-based catalyst remained in a metallic state at CO2RR-relevant potentials and demonstrated a consistent product selectivity regardless of CO 2 concentration. These findings highlight how varying the CO 2 inlet gas concentrations affects the chemical state of catalysts and the resulting performance metrics.

42 ENGINEERING↗

Cobalt oxide-coated N- and B-doped graphene hollow spheres as bifunctional electrocatalysts for oxygen reduction and oxygen evolution reactions

Here, a simple and scalable method has been developed for the synthesis of Co 3 O 4 -coated N- and B-doped graphene hollow spheres (Co 3 O 4 /NBGHSs). These Co 3 O 4 /NBGHSs are highly active for both oxygen reduction and evolution reactions and can exhibit higher electrocatalytic activities and better durability than commercial Pt/C and RuO 2 /C, respectively, demonstrating them to be efficient bi-functional electrocatalysts. In-depth analysis shows that the coupling between Co 3 O 4 and NBGHSs, strong interaction with adsorbed O 2 , high electric conductivity, and the specific hollow structure play important roles in imparting the higher electrocatalytic activities to the Co 3 O 4 /NBGHSs. When tested as cathode catalysts for Zn–air batteries, the Co 3 O 4 /NBGHSs exhibit better performance and higher stability than the Pt/C catalyst and other catalysts reported previously. Lastly, this strongly suggests that the Co 3 O 4 /NBGHSs could be used as efficient electrocatalysts for metal–air batteries with great potential to replace precious metal/carbon based materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics of Hydrogen Generation from In-Situ Methane Pyrolysis: Enhanced by Electromagnetic Heating and Natural Catalysts of Reservoir Rocks

Catalytic pyrolysis of methane (CH4) is a promising approach to generate hydrogen (H2). The apparent activation energy of this process has a significant influence on the efficiency and required temperature for H2 generation. Preliminary experiments indicate that minerals present in shales have catalytic effects during in-situ H2 generation from shale reservoirs under electromagnetic (EM) heating. However, the quantitative role of such natural catalysts on apparent activation energy is not explored yet. This research evaluated the role of reservoir rock (shale) in EM heating and on the apparent activation energy of methane pyrolysis (MP) for in-situ H2 generation. Experiments are conducted in a customized EM reactor with frequency 2.45 GHz, and reaction temperature and generated gases are measured by a real-time IR pyrometer and gas analyzer, respectively. It is found that shale samples experienced thermal runway (TR) at 420 ºC under 0.15 kW EM power without any artificial heating promoter. In the presence of spent shale, CH4 conversion started approximately at 600 ºC with negligible amount of carbon dioxide (CO2) generated during this process. We further calculated apparent reaction order and apparent activation energy for MP process in the presence of shale under EM heating, which are 0.4357 and 98.12 kJ/mol, respectively. This research paves a way for leveraging the role of minerals as natural catalysts for enhancing H2 generation under EM heating in petroleum reservoirs.

02 PETROLEUM↗

Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

Over the past several years, metal-organic framework (MOF)-derived platinum group metal free (PGM-free) electrocatalysts have gained considerable attention due to their high efficiency and low cost as potential replacement for platinum in catalyzing oxygen reduction reaction (ORR). In this review, we summarize the recent advancements in design, synthesis and characterization of MOF-derived ORR catalysts and their performances in acidic and alkaline media. As a result, we also discuss the key challenges such as durability and activity enhancement critical in moving forward this emerging electrocatalyst science.

36 MATERIALS SCIENCE↗

Face-centered tetragonal (FCT) Fe and Co alloys of Pt as catalysts for the oxygen reduction reaction (ORR): A DFT study

Proton exchange membrane fuel cells (PEMFCs) are promising candidates for alternate energy conversion devices owing to their various advantages including high efficiency, reliability, and environmental friendliness. The performance of PEMFCs is fundamentally limited by the sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode. Various studies have addressed myriads of Pt-based alloys as potential catalysts for ORR. However, most of these studies only focus on the cubic-structured Pt-based alloys which require further improvements especially in terms of stability and required loading. We perform first-principle density functional theory calculations to explore Fe and Co alloys of Pt in a different face centered tetragonal (L1 0 ) geometry as potential catalysts for ORR. The work focuses on understanding the reaction mechanism of ORR by both dissociative and associative mechanisms on L1 0 –FePt/Pt(111) and L1 0 –CoPt/Pt(111) surfaces. The binding pattern of each reaction intermediate is studied along with the complete reaction free energy landscape as a function of Pt overlayers. The L1 0 –FePt/Pt(111) and L1 0 –CoPt/Pt(111) surfaces show higher calculated surface activity for ORR as compared to the native fcc Pt(111) surface. The decrease in the required overpotential (η) for the alloys with respect to the unstrained Pt(111) surface is found to be in the range (0.04 V–0.25 V) assuming the dissociative mechanism and (0.02 V–0.10 V) assuming the associative mechanism, where the variation depends on the thickness of Pt overlayers. We further correlate the binding behavior of the reaction intermediates to the applied biaxial strain on the Pt(111) surface with the help of a mechanical eigenforce model. The eigenforce model gives a (semi-) quantitative prediction of the binding energies of the ORR intermediates under applied biaxial strain. The numerical values of the limiting potential (U L ) obtained from the eigenforce model are found to be very close to ones obtained from electronic structure calculations (less than 0.1 V difference). Finally, the eigenforce model is further used to predict the ideal equi-biaxial strain range required on Pt(111) surfaces for optimum ORR activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Component Development for Alkaline URFCs

Performance, cost, and durability of the catalyst materials are the key factors that govern commercialization of H 2 -based energy conversion devices such as unitized regenerative fuel cells (URFCs). Compared to existing battery systems, URFCs offer superior energy density and performance over prolonged operation. In addition, alkaline URFC systems, can utilize low-cost platinum group metal-free (PGM-free) catalysts, resulting in much lower overall system costs. This project seeks to address the major obstacles faced in URFC systems such as cost and efficiency and establish a URFC technical capability through the strategic partnership between UofSC and SRNL. The research focuses on the development of low-PGM and PGM-free based bifunctional oxygen catalysts and electrodes, as well as the development of a URFC testing capability at SRNL.

25 ENERGY STORAGE↗

Size dependence of photocatalytic hydrogen generation for CdTe quantum dots

CdTe quantum dots (QDs) are attractive photosensitizers for photocatalytic proton reduction due to their broad absorbance profile that can extend from the ultraviolet to near-infrared regions, providing access to a larger portion of the solar spectrum than possible with analogous CdSe and CdS QD photosensitizers. Here, the photocatalytic hydrogen (H 2 ) generation from various sizes of dihydrolipoic acid (DHLA)-capped CdTe QDs, ranging from 2.5 to 7.5 nm in diameter, and a molecular Ni-DHLA catalyst in aqueous solutions was evaluated, and an unusual size-dependent photocatalytic activity with CdTe QDs was observed. Under optimized conditions, using 3.4 nm CdTe-DHLA and a 1:20 ratio of QD/Ni-DHLA catalyst, as many as 38 000 turnover numbers (mol H 2 per mol QD) were achieved. However, below this critical size, the H 2 production efficiency decreased; this behavior is attributed to the rapid oxidation of the QD surface, resulting in detrimental surface trap states. These results are consistent with ultrafast transient absorption spectroscopic measurements, which suggest the presence of extremely fast charge-trapping processes in the oxidized CdTe-DHLA QDs. While fast electron transfer from CdTe-DHLA QDs is observed in the presence of the Ni-DHLA catalyst, the charge trapping processes occur on a competitive time scale, thus lowering the efficiency of the CdTe/Ni-DHLA H 2 production system. Understanding rapid charge trapping in CdTe QDs may help suggest potential improvements for the overall CdTe photocatalytic system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoelectrochemical CO 2 Reduction to CO Enabled by a Molecular Catalyst Attached to High-Surface-Area Porous Silicon

A high-surface-area p-type porous Si photocathode containing a covalently immobilized molecular Re catalyst is highly selective for the photoelectrochemical conversion of CO 2 to CO. It gives Faradaic efficiencies of up to 90% for CO at potentials of –1.7 V (versus ferrocenium/ferrocene) under 1 sun illumination in an acetonitrile solution containing phenol. Here, the photovoltage is approximately 300 mV based on comparisons with similar n-type porous Si cathodes in the dark. Using an estimate of the equilibrium potential for CO 2 reduction to CO under optimized reaction conditions, photoelectrolysis was performed at a small overpotential, and the onset of electrocatalysis in cyclic voltammograms occurred at a modest underpotential. The porous Si photoelectrode is more stable and selective for CO production than the photoelectrode generated by attaching the same Re catalyst to a planar Si wafer. Further, facile characterization of the porous Si-based photoelectrodes using transmission mode FTIR spectroscopy leads to highly reproducible catalytic performance.

14 SOLAR ENERGY↗

Aerobic oxidative esterification of primary alcohols over Pd-Au bimetallic catalysts supported on mesoporous silica nanoparticles

Here we have prepared a series of mesoporous silica nanoparticle (MSN) supported Pd-Au bimetallic catalysts using a newly developed sequential impregnation method. These catalysts were fully characterized by various techniques including nitrogen sorption, powder X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy (TEM) and high angle annular dark-field scanning transmission electron microscopy (HADDF-STEM). By using this synthetic approach, we observed metal nanoparticles (NP) with diameters of 1–2 nm homogeneously supported on the MSN. The catalytic performance of these MSN supported metal NPs was tested by aerobic oxidative esterification in a tandem reaction where primary alcohols are oxidized to their corresponding aldehydes and to esters in a subsequent reaction. We determined that Pd NPs are very efficient in the first step of oxidation; however, stagnant in the subsequent oxidation. On the contrary, Au NPs show slow reactivity in converting alcohols to aldehydes, but extraordinarily efficient in the oxidation of aldehydes to esters. By fine tuning the metal ratio, the bimetallic catalyst exhibits better reactivity and selectivity toward a variety of primary alcohols than the corresponding monometallic catalysts. In addition, we also found that the bimetallic Pd-Au@MSN catalysts can be recycled three times without a significant loss in activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Designing a Zn–Ag Catalyst Matrix and Electrolyzer System for CO 2 Conversion to CO and Beyond

CO 2 emissions can be transformed into high-added-value commodities through CO 2 electrocatalysis; however, efficient low-cost electrocatalysts are needed for global scale-up. Inspired by other emerging technologies, the authors report the development of a gas diffusion electrode containing highly dispersed Ag sites in a low-cost Zn matrix. Here, this catalyst shows unprecedented Ag mass activity for CO production: –614 mA cm –2 at 0.17 mg of Ag. Subsequent electrolyte engineering demonstrates that halide anions can further improve stability and activity of the Zn–Ag catalyst, outperforming pure Ag and Au. Membrane electrode assemblies are constructed and coupled to a microbial process that converts the CO to acetate and ethanol. Combined, these concepts present pathways to design catalysts and systems for CO 2 conversion toward sought-after products.

36 MATERIALS SCIENCE↗

Chapter 3: Nanostructured Iron Oxide Hybrid Composites as Heterogeneous Fenton-Like Catalyst for Remediation of Persistent Organic Pollutants

In water purification research and technologies, heterogeneous Fenton catalysts are evolving as an excellent material recently. A summary of present research on heterogeneous Fenton/Fenton-like processes is essential for developing novel and high-efficiency organic wastewater treatment methods. In this chapter, we discussed the basics of Fenton reactions taking the example of iron oxides and their different composites, such as bimetallic composites, composites with carbon compounds, and Fe metal-organic frameworks (MOFs). The important operating parameters (solution pH, H 2 O 2 dosage, amount of catalyst used, and reaction temperature) in heterogeneous Fenton-like reactions are discussed. Strategies to increase the rate and activities of heterogeneous Fenton catalysts by using energy sources are presented. The mechanistic aspects of heterogeneous Fenton processes and reusability of catalysts along with their application in real wastewater plants are summarized and discussed. Finally, we concluded with the scope and future prospects of heterogeneous Fenton catalysis research to motivate the readers to construct novel and efficient heterogeneous Fenton/Fenton-like systems for industrial applications.

carbon composites↗

Rational Design of Rhodium–Iridium Alloy Nanoparticles as Highly Active Catalysts for Acidic Oxygen Evolution

The oxygen evolution reaction (OER) is pivotal for renewable energy conversion and storage devices, such as water electrolyzers and rechargeable metal–air batteries. However, the rational design of electrocatalysts with suitably high efficiencies and stabilities in strongly acidic electrolytes remains a significant challenge. Here, we show the demonstration of sub-10 nm, composition-tunable Rh–Ir alloy nanoparticles (NPs) prepared using a scalable microwave-assisted method as superior acidic OER catalysts. The OER activities showed a volcano-shaped dependence on Ir composition, with Ir-rich NPs (Ir ≥ 51%) achieving better OER performance than pure Ir NPs, as reflected by lower overpotentials and higher mass activities. Most significantly, Rh 22 Ir 78 NPs achieved a maximum mass activity of 1.17 A mg –1 Ir at a 300 mV overpotential in 0.5 M H 2 SO 4 , which corresponds to a 3-fold enhancement relative to pure Ir NPs, making it one of the most active reported OER catalysts under acidic conditions. Density functional theory calculations reveal that owing to the synergy of ensemble and electronic effects by alloying a small amount of Rh with Ir, the binding energy difference of the O and OOH intermediates is reduced, leading to faster kinetics and enhanced OER activity. Furthermore, Rh–Ir alloy NPs demonstrated excellent durability in strongly acidic electrolyte. Furthermore, this work not only provides fundamental understandings relating to composition–electrochemical performance relationships but also represents the rational design of highly efficient OER electrocatalysts for applications in acidic media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double-Atom Catalysts Featuring Inverse Sandwich Structure for CO 2 Reduction Reaction: A Synergetic First-Principles and Machine Learning Investigation

Electrocatalytic CO 2 reduction reactions (CO 2 RR) based on scalable and highly efficient catalysis provide an attractive strategy for reducing CO 2 emissions. Here in this work, we combined first-principles density functional theory (DFT) and machine learning (ML) to comprehensively explore the potential of double-atom catalysts (DACs) featuring an inverse sandwich structure anchored on defective graphene (gra) to catalyze CO 2 RR to generate C 1 products. We started with five homonuclear M 2 ⊥gra (M = Co, Ni, Rh, Ir, and Pt), followed by 127 heteronuclear MM'⊥gra (M = Co, Ni, Rh, Ir, and Pt, M' = Sc–Au). Stable DACs were screened by evaluating their binding energy, formation energy, and dissolution potential of metal atoms, as well as conducting first-principles molecular dynamics simulations with and without solvent water molecules. Based on DFT calculations, Rh 2 ⊥gra DAC was found to outperform the other four homonuclear DACs and the Rh-based single- and double-atom catalysts of noninverse sandwich structures. Out of the 127 heteronuclear DACs, 14 were found to be stable and have good catalytic performance. An ML approach was adopted to correlate key factors with the activity and stability of the DACs, including the sum of radii of metal and ligand atoms (d M–M' , d M–C , and d M'–C ), the sum and difference of electronegativity of two metal atoms (P M + P M' , P M – P M '), the sum and difference of first ionization energy of two metal atoms (I M + I M' , I M – I M '), the sum and difference of electron affinity of two metal atoms (A M + A M' , A M – A M '), and the number of d-electrons of the two metal atoms (Nd). The obtained ML models were further used to predict 154 potential electrocatalysts out of 784 possible DACs featuring the same inverse sandwich configuration. Overall, this work not only identified promising CO 2 RR DACs featuring the reported inverse sandwich structure but also provided insights into key atomic characteristics associated with high CO 2 RR activity.

30 DIRECT ENERGY CONVERSION↗

Oxygen Reduction at Very Low Overpotential on Nanoporous Ag Catalysts

Here we report a monolithic nanoporous Ag (np-Ag) material, synthesized using the dealloying method, as high-performance catalysts for ORR in alkaline media. As shown in Scheme 1, when there is insufficient potential input, the O 2 molecules are more likely to rebound off from a planar electrode surface (i.e. bulk polycrystalline metal, films made from nanoparticles or nanowires) before they could be reduced. In contrast, they are more likely to be trapped inside the monolithic nanoporous structure, contacting with catalytic surface for multiple time, which greatly enhances the chance for them to be fully reduced. As a result, the np-Ag catalyst is able to achieve an equivalent or better ORR performance than the state-of the-art Pt/C catalyst at low overpotentials, which is most desired in electrochemical energy applications for maximizing efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the Interface of Skin-Layered Titanium Fibers for Electrochemical Water Splitting

Water electrolysis is the key to a decarbonized energy system, as it enables the conversion and storage of renewably generated intermittent electricity in the form of hydrogen. However, reliability challenges arising from titanium-based porous transport layers (PTLs) have hitherto restricted the deployment of next-generation water-splitting devices. Here, it is shown for the first time how PTLs can be adapted so that their interface remains well protected and resistant to corrosion across ˜4000 h under real electrolysis conditions. It is also demonstrated that the malfunctioning of unprotected PTLs is a result triggered by additional fatal degradation mechanisms over the anodic catalyst layer beyond the impacts expected from iridium oxide stability. Now, superior durability and efficiency in water electrolyzers can be achieved over extended periods of operation with less-expensive PTLs with proper protection, which can be explained by the detailed reconstruction of the interface between the different elements, materials, layers, and components presented in this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗