Co-pyrolysis of wood chips and bentonite/kaolin: Influence of temperatures and minerals on characteristics and carbon sequestration potential of biochar.

Biochars have been highlighted as a means of carbon sequestration, which is significant for achieving carbon neutrality. Mixtures of wood chips and either bentonite or kaolin were co-pyrolysed at temperatures of 350 °C and 550 °C, and the microstructural characteristics and the carbon sequestration potential of the resultant biochar were explored in the study. The addition of minerals promoted the formation of a stable carbon structure in biochar, especially the proportion of SiC bonds in the high-temperature mineral-composited biochar increased by 3.56-3.82 times compared with the original biochar. After bentonite or kaolin was added to wood chips pyrolysed at 550 °C, the carbon loss after H2O2 oxidation was reduced to no more than 19.2%, and the Recalcitrance Index (R50) of biochar increased to no less than 0.89. The combined action of high temperature and minerals promoted the formation of highly aromatic structures of biochar (H:C < 0.4) and reduced the amount of dissolved organic carbon to 4.89 mg g-1. Furthermore, minerals directly covered the surface of biochar, and the content of SiC bond increased, thus strengthening the chemical and thermal stability of biochar. However, the addition of minerals had no significant effect on the biological stability of biochar. The study indicates that the pre-pyrolysis mineral addition is an effective way to increase the carbon sequestration potential of biochar.

Mesoporous Biopolymer Architecture Enhanced the Adsorption and Selectivity of Aqueous Heavy-Metal Ions.

Halloysite nanotubes (HNT) and ball-milled biochar (BC) incorporated biocompatible mesoporous adsorbents (HNT-BC@Alg) were synthesized for adsorption of aqueous heavy-metal ions. HNT-BC@Alg outperformed the BC, HNT, and BC@Alg in removing cadmium (Cd), copper (Cu), nickel (Ni), and lead (Pb). Mesoporous structure (∼7.19 to 7.56 nm) of HNT-BC@Alg was developed containing an abundance of functional groups induced from encapsulated BC and tubular HNT, which allowed heavy metals to infiltrate and interact with the adsorbents. Siloxane groups from HNT, oxygen-containing functional groups from BC, and hydroxyl and carboxyl groups from alginate polymer play a significant role in the adsorption of heavy-metal ions. The removal percentage of heavy metals was recorded as Pb (∼99.97 to 99.05%) > Cu (∼95.01 to 90.53%) > Cd (∼92.5 to 55.25%) > Ni (∼80.85 to 50.6%), even in the presence of 0.01/0.001 M of CaCl2 and Na2SO4 as background electrolytes and charged organic molecule under an environmentally relevant concentration (200 µg/L). The maximum adsorption capacities of Ni, Cd, Cu, and Pb were calculated as 2.85 ± 0.08, 6.96 ± 0.31, 16.87 ± 1.50, and 26.49 ± 2.04 mg/g, respectively. HNT-BC@Alg has fast sorption kinetics and maximum adsorption capacity within a short contact time (∼2 h). Energy-dispersive X-ray spectroscopy (EDS) elemental mapping exhibited that adsorbed heavy metals co-distributed with Ca, Si, and Al. The reduction of surface area, pore volume, and pore area of HNT-BC@Alg (after sorption of heavy metals) confirms that mesoporous surface (2-18 nm) supports diffusion, infiltration, and interaction. However, a lower range of mesoporous diameter of the adsorbent is more suitable for the adsorption of heavy-metal ions. The adsorption isotherm and kinetics fitted well with the Langmuir isotherm and the pseudo-second-order kinetic models, demonstrating the monolayer formation of heavy-metal ions through both the physical sorption and chemical sorption, including pore filling, ion exchange, and electrostatic interaction.

Fabrication of highly and poorly oxidized silver oxide/silver/tin(IV) oxide nanocomposites and their comparative anti-pathogenic properties towards hazardous food pathogens.

Herein, we report the fabrication of highly oxidized silver oxide/silver/tin(IV) oxide (HOSBTO or Ag3+-enriched AgO/Ag/SnO2) nanocomposite under a robust oxidative environment created with the use of concentrated nitric acid. Tin(IV) hydroxide nanofluid is added to the reaction mixture as a stabilizer for the Ag3+-enriched silver oxide in the nanocomposite. The formation of Ag nanoparticles in this nanocomposite originates from the decomposition of silver oxides during calcination at 600 °C. For comparison, poorly oxidized silver oxide/silver/tin(IV) oxide (POSBTO with formula AgO/Ag/SnO2) nanocomposite has also been prepared by following the same synthetic procedures, except for the use of concentrated nitric acid. Finally, we studied in detail the anti-pathogenic capabilities of both nanocomposites against four hazardous pathogens, including pathogenic fish bacterium (Stenotrophomonas maltophilia stain EP10), oomycete (Phytophthora cactorum strain P-25), and two different strains of pathogenic strawberry fungus, BRSP08 and BRSP09 (Collectotrichum siamense). The bioassays reveal that the as-prepared HOSBTO and POSBTO nanocomposites exhibit significant inhibitory activities against the tested pathogenic bacterium, oomycete, and fungus in a dose-dependent manner. However, the degree of dose-dependent effectiveness of the two nanocomposites against each pathogen largely varies.

Unsaturated p-Metal-Based Metal-Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions.

Electrochemical ammonia synthesis that utilizes renewable electricity in the nitrogen reduction reaction (NRR) has recently been remarkably considered. Of particular importance is to develop efficient electrocatalysts at low costs. Herein, highly selective nitrogen capture using porous aluminum-based metal-organic frameworks (MOFs) materials, MIL-100 (Al), is first designed for the electrochemical nitrogen fixation in alkaline media under ambient conditions. Owing to the unique structure, MIL-100 (Al) exhibits remarkable NRR properties (NH3 yield: 10.6 µg h-1 cm-2 mgcat.-1 and Faradaic efficiency: 22.6%) at a low overpotential (177 mV). Investigation indicates that the catalyst shows excellent N2-selective captures due to the unsaturated metal sites binding with N2. More specifically, as the Al 3p band can strongly interact with N 2p orbitals, Al as a main group metal presents a high and selective affinity to N2. The utilization of multifunctional MOF catalysts delivers both high N2 selectivity and abundant catalytic sites, resulting in remarkable efficiency for NH3 production.

Biochar-based fertilizer: Supercharging root membrane potential and biomass yield of rice.

Biochar-based compound fertilizers (BCF) and amendments have proven to enhance crop yields and modify soil properties (pH, nutrients, organic matter, structure etc.) and are now in commercial production in China. While there is a good understanding of the changes in soil properties following biochar addition, the interactions within the rhizosphere remain largely unstudied, with benefits to yield observed beyond the changes in soil properties alone. We investigated the rhizosphere interactions following the addition of an activated wheat straw BCF at an application rates of 0.25% (g·g-1 soil), which could potentially explain the increase of plant biomass (by 67%), herbage N (by 40%) and P (by 46%) uptake in the rice plants grown in the BCF-treated soil, compared to the rice plants grown in the soil with conventional fertilizer alone. Examination of the roots revealed that micron and submicron-sized biochar were embedded in the plaque layer. BCF increased soil Eh by 85 mV and increased the potential difference between the rhizosphere soil and the root membrane by 65 mV. This increased potential difference lowered the free energy required for root nutrient accumulation, potentially explaining greater plant nutrient content and biomass. We also demonstrate an increased abundance of plant-growth promoting bacteria and fungi in the rhizosphere. We suggest that the redox properties of the biochar cause major changes in electron status of rhizosphere soils that drive the observed agronomic benefits.

Transition Metal Aluminum Boride as a New Candidate for Ambient-Condition Electrochemical Ammonia Synthesis.

Achieving more meaningful N2 conversion by reducing the energy input and carbon footprint is now being investigated through a method of N2 fixation instead of the Haber-Bosch process. Unfortunately, the electrochemical N2 reduction reaction (NRR) method as a rising approach currently still shows low selectivity (Faradaic efficiency < 10%) and high-energy consumption [applied potential at least - 0.2 V versus the reversible hydrogen electrode (RHE)]. Here, the role of molybdenum aluminum boride single crystals, belonging to a family of ternary transition metal aluminum borides known as MAB phases, is reported for the electrochemical NRR for the first time, at a low applied potential (- 0.05 V versus RHE) under ambient conditions and in alkaline media. Due to the unique nano-laminated crystal structure of the MAB phase, these inexpensive materials have been found to exhibit excellent electrocatalytic performances (NH3 yield: 9.2 µg h-1 cm-2 mg cat. -1 , Faradaic efficiency: 30.1%) at the low overpotential, and to display a high chemical stability and sustained catalytic performance. In conjunction, further mechanism studies indicate B and Al as main-group metals show a highly selective affinity to N2 due to the strong interaction between the B 2p/Al 3p band and the N 2p orbitals, while Mo exhibits specific catalytic activity toward the subsequent reduction reaction. Overall, the MAB-phase catalyst under the synergy of the elements within ternary compound can suppress the hydrogen evolution reaction and achieve enhanced NRR performance. The significance of this work is to provide a promising candidate in the future synthesis of ammonia.

Passivation by pyridine-induced PbI2 in methylammonium lead iodide perovskites.

Defects at discontinuities of the perovskite lattice limit the performance of the perovskite solar cell (PSC). Lead iodide (PbI2) and pyridine have been shown to passivate these defects. We treat methylammonium lead iodide (MAPbI3) films with pyridine solutions to investigate the effects of the two passivators. By comparing confocal fluorescence microscopy (CFM) images at 405 nm excitation and then at 559 nm excitation we demonstrate the pyridine treatment passivates and forms PbI2 crystallites which cause additional passivation.

Physical characteristics of capacitive carbons derived from the electrolytic reduction of alkali metal carbonate molten salts.

Carbons have been synthesized through the reduction of molten carbonate systems under varied conditions. The mechanism and kinetics of carbon electrodeposition has been investigated. Carbon morphologies include amorphous, graphite-like, and spherical aggregate phases. Increased graphitic character is observed in carbons electrodeposited at more cathodic potentials, particularly at higher temperatures. Bonding has been investigated and oxygen functionalised sp2 and sp3 structures have been identified. The level of functionalization decreases in carbons with reduced amorphous and increased graphitic character. Thermal decomposition of electrodepositied carbons has been investigated and zero order kinetics have been identified. A relationship has been identified between elevated oxygen functionalization and increased pseudo-capacitance, with carbons deposited at 0.15 A cm-2 showing capacitances of 400 F g-1 in 0.5 M H2SO4 at sweep rates of 10 mV s-1.

Microstructural and associated chemical changes during the composting of a high temperature biochar: Mechanisms for nitrate, phosphate and other nutrient retention and release.

Recent studies have demonstrated the importance of the nutrient status of biochar and soils prior to its inclusion in particular agricultural systems. Pre-treatment of nutrient-reactive biochar, where nutrients are loaded into pores and onto surfaces, gives improved yield outcomes compared to untreated biochar. In this study we have used a wide selection of spectroscopic and microscopic techniques to investigate the mechanisms of nutrient retention in a high temperature wood biochar, which had negative effects on Chenopodium quinoa above ground biomass yield when applied to the system without prior nutrient loading, but positive effects when applied after composting. We have compared non-composted biochar (BC) with composted biochar (BCC) to elucidate the differences which may have led to these results. The results of our investigation provide evidence for a complex series of reactions during composting, where dissolved nutrients are first taken up into biochar pores along a concentration gradient and through capillary action, followed by surface sorption and retention processes which block biochar pores and result in deposition of a nutrient-rich organomineral (plaque) layer. The lack of such pretreatment in the BC samples would render it reactive towards nutrients in a soil-fertilizer system, making it a competitor for, rather than provider of, nutrients for plant growth.

Thermal stability of biochar and its effects on cadmium sorption capacity.

In this study, the thermal stability of a wood shaving biochar (WS, 650°C), a chicken litter biochar (CL, 550°C) and an activated carbon (AC, 1100°C) were evaluated by combustion at 375°C for 24h to remove the labile non-carbonized organic matter. Results showed that WS and CL biochars were not thermally stable and can lose most of the organic C during combustion. The combusted WS and CL biochars retained considerable amounts of negative charge and displayed higher sorption for Cd (from 5.46 to 68.9mg/g for WS and from 48.5 to 60.9mg/g for CL). The AC retained 76.5% of its original C and became more negatively chargely after combustion, but its sorption for Cd slightly decreased (from 18.5 to 14.9mg/g). This study indicated that after potential burning in wildfires (200-500°C), biochars could have higher sorption capacity for metals by remaining minerals.

Pyrolysis of attapulgite clay blended with yak dung enhances pasture growth and soil health: Characterization and initial field trials.

Recent studies have shown that the pyrolysis of biomass combined with clay can result in both lower cost and increase in plant yields. One of the major sources of nutrients for pasture growth, as well as fuel and building materials in Tibet is yak dung. This paper reports on the initial field testing in a pasture setting in Tibet using yak dung, biochar, and attapulgite clay/yak dung biochars produced at ratios of 10/90 and 50/50 clay to dung. We found that the treatment with attapulgite clay/yak dung (50/50) biochar resulted in the highest pasture yields and grass nutrition quality. We also measured the properties and yields of mixtures of clay/yak dung biochar used in the field trials produced at 400°C and 500°C to help determine a possible optimum final pyrolysis temperature and dung/clay ratio. It was observed that increasing clay content increased carbon stability, overall biochar yield, pore size, carboxyl and ketone/aldehyde functional groups, hematite and ferrous/ferric sulphate/thiosulphate concentration, surface area and magnetic moment. Decreasing clay content resulted in higher pH, CEC, N content and an enhanced ability to accept and donate electrons. The resulting properties were a complex function of both processing temperature and the percentage of clay for the biochars processed at both 400°C and 500°C. It is possible that the increase in yield and nutrient uptake in the field trial is related to the higher concentration of C/O functional groups, higher surface area and pore volume and higher content of Fe/O/S nanoparticles of multiple oxidation state in the 50/50 clay/dung. These properties have been found to significantly increase the abundance of beneficial microorganisms and hence improve the nutrient cycling and availability in soil. Further field trials are required to determine the optimum pyrolysis production conditions and application rate on the abundance of beneficial microorganisms, yields and nutrient quality.

Chemolithotrophic processes in the bacterial communities on the surface of mineral-enriched biochars.

Biochar and mineral-enriched biochar (MEB) have been used as soil amendments to improve soil fertility, sequester carbon and mitigate greenhouse gas emissions. Such beneficial outcomes could be partially mediated by soil bacteria, however little is known about how they directly interact with biochar or MEB. We therefore analyzed the diversity and functions of bacterial communities on the surfaces of one biochar and two different MEBs after a 140-day incubation in soil. The results show that the biochar and the MEBs harbor distinct bacterial communities to the bulk soil. Communities on biochar and MEBs were dominated by a novel Gammaproteobacterium. Genome reconstruction combined with electron microscopy and high-resolution elemental analysis revealed that the bacterium generates energy from the oxidation of iron that is present on the surface. Two other bacteria belonging to the genus Thiobacillus and a novel group within the Oxalbacteraceae were enriched only on the MEBs and they had the genetic capacity for thiosulfate oxidation. All three surface-enriched bacteria also had the capacity to fix carbon dioxide, either in a potentially strictly autotrophic or mixotrophic manner. Our results show the dominance of chemolithotrophic processes on the surface of biochar and MEB that can contribute to carbon sequestration in soil.

Mineral-Biochar Composites: Molecular Structure and Porosity.

Dramatic changes in molecular structure, degradation pathway, and porosity of biochar are observed at pyrolysis temperatures ranging from 250 to 550 °C when bamboo biomass is pretreated by iron-sulfate-clay slurries (iron-clay biochar), as compared to untreated bamboo biochar. Electron microscopy analysis of the biochar reveals the infusion of mineral species into the pores of the biochar and the formation of mineral nanostructures. Quantitative (13)C nuclear magnetic resonance (NMR) spectroscopy shows that the presence of the iron clay prevents degradation of the cellulosic fraction at pyrolysis temperatures of 250 °C, whereas at higher temperatures (350-550 °C), the clay promotes biomass degradation, resulting in an increase in both the concentrations of condensed aromatic, acidic, and phenolic carbon species. The porosity of the biochar, as measured by NMR cryoporosimetry, is altered by the iron-clay pretreatment. In the presence of the clay, at lower pyrolysis temperatures, the biochar develops a higher pore volume, while at higher temperature, the presence of clay causes a reduction in the biochar pore volume. The most dramatic reduction in pore volume is observed in the kaolinite-infiltrated biochar at 550 °C, which is attributed to the blocking of the mesopores (2-50 nm pore) by the nonporous metakaolinite formed from kaolinite.

Preparation and Binding Evaluation of Histamine-Imprinted Microspheres via Conventional Thermal and RAFT-Mediated Free-Radical Polymerization.

Elevated histamine (HTM) levels are closely linked to food poisoning as well as to pathophysiological allergic diseases. In this study, HTM-imprinted, solution-processable microspheres were prepared via high-dilution conventional thermal polymerization (CTP) and controlled radical polymerization (CRP) using ethylene glycol dimethacrylate (80 or 90 wt %) and methacrylic acid at 60 °C in acetonitrile and evaluated as recognition materials for sensing applications. The polymers were selective to HTM in binding studies, cross-rebinding, and competitive binding assays against the HTM analogues histidine, imidazole, and tryptamine. The selective binding capacity was significantly higher with CTP-80 (on the basis of mass: 21.0 µmol/g and surface area: 8.08 × 10-2 µmol/m2) than that with both CTP-90 (8.47 µmol/g, 4.49 × 10-2 µmol/m2) and CRP-80 (9.00 µmol/g, 1.19 × 10-2 µmol/m2).

A three-year experiment confirms continuous immobilization of cadmium and lead in contaminated paddy field with biochar amendment.

Heavy metal contamination in croplands has been a serious concern because of its high health risk through soil-food chain transfer. A field experiment was conducted in 2010-2012 in a contaminated rice paddy in southern China to determine if bioavailability of soil Cd and Pb could be reduced while grain yield was sustained over 3 years after a single soil amendment of wheat straw biochar. Contaminated biochar particles were separated from the biochar amended soil and microscopically analyzed to help determine where, and how, metals were immobilized with biochar. Biochar soil amendment (BSA) consistently and significantly increased soil pH, total organic carbon and decreased soil extractable Cd and Pb over the 3 year period. While rice plant tissues' Cd content was significantly reduced, depending on biochar application rate, reduction in plant Pb concentration was found only in root tissue. Analysis of the fresh and contaminated biochar particles indicated that Cd and Pb had probably been bonded with the mineral phases of Al, Fe and P on and around and inside the contaminated biochar particle. Immobilization of the Pb and Cd also occurred to cation exchange on the porous carbon structure.

Potassium accumulation between type I hair cells and calyx terminals in mouse crista.

The mode of synaptic transmission in the vestibular periphery, between type I hair cells and their associated calyx terminal, has been the subject of much debate. The close and extensive apposition of pre- and post-synaptic elements has led some to suggest potassium (K(+)) accumulates in the intercellular space and even plays a role in synaptic transmission. During patch clamp recordings from isolated and embedded hair cells in a semi-intact preparation of the mouse cristae, we noted marked differences in whole-cell currents. Embedded type I hair cells show a prominent droop during steady-state activation as well as a dramatic collapse in tail currents. Responses to a depolarizing voltage step (-124 to +16 mV) in embedded, but not isolated, hair cells resulted in a >40 mV shift of the K(+) equilibrium potential and a rise in effective K(+) concentration (>50 mM) in the intercellular space. Together these data suggest K(+) accumulation in the intercellular space accounts for the different responses in isolated and embedded type I hair cells. To test this notion, we exposed the preparation to hyperosmotic solutions to enlarge the intercellular space. As predicted, the K(+) accumulation effects were reduced; however, a fit of our data with a classic diffusion model suggested K(+) permeability, rather than the intercellular space, had been altered by the hyperosmotic change. These results support the notion that under depolarizing conditions substantial K(+) accumulation occurs in the space between type I hair cells and calyx. The extent of K(+) accumulation during normal synaptic transmission, however, remains to be determined.

The spermostatic and microbicidal actions of quinones and maleimides: toward a dual-purpose contraceptive agent.

There is an urgent need to develop safe, effective, dual-purpose contraceptive agents that combine the prevention of pregnancy with protection against sexually transmitted diseases. Here we report the identification of a group of compounds that on contact with human spermatozoa induce a state of "spermostasis," characterized by the extremely rapid inhibition of sperm movement without compromising cell viability. These spermostatic agents were more active and significantly less toxic than the reagent in current clinical use, nonoxynol 9, giving therapeutic indices (ratio of spermostatic to cytotoxic activity) that were orders of magnitude greater than this traditional spermicide. Although certain compounds could trigger reactive oxygen species generation by spermatozoa, this activity was not correlated with spermostasis. Rather, the latter was associated with alkylation of two major sperm tail proteins that were identified as A Kinase-Anchoring Proteins (AKAP3 and AKAP4) by mass spectrometry. As a consequence of disrupted AKAP function, the abilities of cAMP to drive protein kinase A-dependent activities in the sperm tail, such as the activation of SRC and the consequent stimulation of tyrosine phosphorylation, were suppressed. Furthermore, analysis of microbicidal activity using Chlamydia muridarum revealed powerful inhibitory effects at the same low micromolar doses that suppressed sperm movement. In this case, the microbicidal action was associated with alkylation of Major Outer Membrane Protein (MOMP), a major chlamydial membrane protein. Taken together, these results have identified for the first time a novel set of cellular targets and chemical principles capable of providing simultaneous defense against both fertility and the spread of sexually transmitted disease.

Surface characterisation of chemically reduced electrolytic manganese dioxide.

In this work a titration technique has been used to characterize the amphoteric surface properties of a series of chemically reduced electrolytic manganese dioxide (EMD) samples (MnO 1.97 to MnO 1.50). The surface of the EMD was found to consist of independent acidic and basic hydroxyl groups, which were able to be characterised by their respective equilibrium constants and site concentrations. For this chemically reduced series Kb varied from (1.81-8.43)x10(-10) as reduction proceeded, with the corresponding basic site concentration varying from (0.20-2.50)x10(-4) mol/m2 over the pH range considered. Ka was ranged from (1.23-9.23)x10(-6) over the reduction range considered. The increase in Kb suggested a weakening of the MnO bond via the introduction of the larger Mn3+ ions which will increase the length of this bond. Weakening the MnO bond results in a corresponding strengthening of the OH bond giving the surface hydroxyl group a basic nature which is supported by the increasing basic site concentration. For the samples with an x in MnOx value above 1.71 the total number of acidic sites decreased which supports the increase in the concentration of basic sites; however, below 1.71, the surface concentration of acidic sites increases slightly, which can be rationalised by the fact that the pyrolusite domains within the EMD (with relatively stronger MnO bonds) are accessible at this stage of the reduction. The number of surface oxide sites (Ns) and surface hydroxyl sites (Ns(OH)) were calculated crystallographically, and from the sum of the acid and basic hydroxyl groups determined by titration. Both methods produced data with the same order of magnitude, as well as indicated the expected increase in the number of surface hydroxyl groups with increasing degree of reduction. Electrochemical analysis of the samples in 9 M KOH showed the expected decrease in capacity with an increase in the degree of reduction. It also showed a decrease in the amount of charge contributed to the overall homogeneous reduction by Mn4+ ions in surface defects and within the ramsdellite domains over the entire x in MnOx range. However, the amount of charge contributed from the pyrolusite domains remained unchanged until after a x in MnOx value of 1.71.

Surface characterization of heat-treated electrolytic manganese dioxide.

In this work a titration technique was used to determine the amphoteric surface properties of a series of heat-treated electrolytic manganese dioxide (EMD) samples (up to 500 degrees C). The surface of each sample was found to consist of independent acidic and basic hydroxyl sites, which could be characterized by their respective equilibrium constants and site concentrations. It was found that the acidic sites could not be characterized by a single equilibrium constant, but rather by a distribution indicating the subtle differences between individual sites, while a single equilibrium constant adequately represented the basic sites. For EMD, K(a) varied between 0.1 and 6.3x10(-5), with a corresponding [MnOH((a)T)] value varying between 9.1 and 6.4x10(-6) mol m(-2) over the pH range considered. K(b) and [MnOH((b)T)] were found to be 1.81x10(-9) and 1.93x10(-5) mol m(-2), respectively. With heat treatment, K(a) increased, suggesting a strengthening of the MnO bond via the removal of defects such as Mn(3+) ions and cation vacancies. The fact that K(b) also increased was initially counterintuitive because it suggested that the MnO bond had been weakened by heat treatment. However, assuming that the acidic and basic hydroxyl groups are independent, the trends in K(b) could be rationalized in terms of oxygen ion coordination in the progressively heat-treated samples. The number of surface sites (N(s)) was determined crystallographically and from the sum [MnOH((a)T)] + [MnOH((b)T)]. The data from both methods were of the same order of magnitude but exhibited different trends due to certain inadequacies in both methods. However, the data trends did indicate that the crystal planes at the particle surface could be changing with heat treatment due to a decrease in the value of N(s) determined from the surface titrations. Electrochemical analysis of the samples in 9 M KOH indicated that their performance degraded considerably with heat treatment. In comparison with the surface titration data, it was concluded that proton insertion into the structure occurred only through basic surface sites, the decreasing number of which could limit performance.