OH Concentration Research Articles

Cavity-enhanced Faraday rotation spectroscopy for interference-free measurement of OH radical at 2.8 μm

An instrument based on cavity-enhanced Faraday rotation spectroscopy (CE-FRS) operating at 2.8 μm has been developed for interference-free measurement of OH radicals in the laboratory. By off-axis coupling of a continuous-wave laser into a high finesse optical cavity, FRS signal is obtained from balanced detection of time-integrated light intensity leaking out of the cavity in the presence of magnetic field. Radio-frequency white noise (5–520 MHz) was injected into laser current which reduced intensity fluctuations in cavity transmission, thus improved the signal-to-noise ratio of the spectroscopic signal by a factor of 2. The setup provides a simple and robust spectroscopic instrument for in-situ and highly-selective detection of paramagnetic species. We demonstrated the instrument’s capabilities using OH radical with concentration in the range of 1012 molecule.cm−3, generated by microwave discharge of water vapor at low pressure. The CE-FRS instrument exhibited a limit of detection of ∼ 1010 molecule.cm−3 in an integration time of 20 s, which is enhanced by a factor of 2.5 compared to cavity-enhanced wavelength modulation spectroscopy involving an off-axis integrated cavity output spectroscopy approach. A time-resolved FRS signal was recorded in a pulsed microwave discharge regime, giving a millisecond time resolution for the measurement of OH concentration profile. The developed instrument provides a potential analytical tool for the measurement of OH concentration for chemical kinetic study in reactor cells.

Reaction between peracetic acid and carbonyl oxide: Quantitative kinetics and insight into implications in the atmosphere

Peracetic acid (PAA, CH3C(O)OOH) is one of the most abundant organic peroxyacid in the atmosphere. PAA is often assumed to be removed by hydroxyl radical in the gas phase of troposphere, but its reaction rate is quite low. Here, we investigated the new reaction between PAA and carbonyl oxide (CH2OO) by using quantum chemical methods, reaction kinetics in combination with atmospheric modeling. We first performed W3X-L calculations close to CCSDT(Q)/CBS accuracy with the reaction systems containing eight carbon and oxygen atoms. The present findings show that the post-CCSD(T) contribution is about 0.50 kcal mol-1, which is important for obtaining quantitative relative enthalpy of activation at 0 K. We find that the recrossing effect reduces the rate constant by an order of magnitude for the mechanism of the hydrogen-shift coupled carbon-oxygen addition at low temperature. The calculated results reveal that the anharmonicity increases the rate constants of CH2OO + CH3C(O)OOH by a factor of 6.27 at 298 K. The present findings uncover that the PAA + CH2OO reaction is a dominant pathway for PAA sinks in the gas phase of troposphere at the lower nighttime OH concentrations at 298 K, since the rate of PAA + CH2OO is even an order of magnitude higher than the rate of the PAA + OH reaction. Moreover, atmospheric modeling simulations unveil that CH2OO can make certain contribution to the reduction of PAA in the Amazon.

Release Behavior of Pb(II) Ions on the Galena Surface: Dissolution Experiment, DFT Calculation, and MD Simulation

In this study, the release behavior of Pb(II) ions from the galena surface and their occurrence forms in the migration process under acid and alkaline conditions were investigated by dissolution experiment, the density functional theory (DFT) calculation, and molecular dynamics (MD) simulation. The dissolution experiments indicated that acidic and high alkaline conditions are more beneficial for the release of Pb(II) rather than neutral and weak alkaline conditions. The quantum chemical calculations indicated that under acidic conditions, H+ can destroy the surface structure of galena, leading to the dissolution of Pb2+ from the mineral surface into the liquid phase. OH− can also damage the galena surface to a certain extent under alkaline conditions. Additionally, MD simulations were further utilized to study the occurrence forms of Pb(II) ions in alkaline solutions. The results suggested that with a certain concentration of OH−, Pb2+ ions will form lead hydroxide aggregates, while excessive OH− could lead to the dispersion and dissolution of the lead hydroxo complexes. The surface morphological observation by SEM can well support the calculation and simulation results.

Black Carbon Radiative Impacts on Surface Atmospheric Oxidants in China with WRF-Chem Simulation

Black carbon (BC) changes the radiative flux in the atmosphere by absorbing solar radiation, influencing photochemistry in the troposphere. To evaluate the seasonal direct radiative effects (DREs) of BC and its influence on surface atmospheric oxidants in China, the WRF-Chem model was utilized in this study. The simulation results suggested that the average annual mean values of the clear-sky DREs of BC at the top of the atmosphere, in the atmosphere and at the surface over China are +2.61, +6.27 and −3.66 W m−2, respectively. Corresponding to the seasonal variations of BC concentrations, the relative changes of the mean surface photolysis rates (J[O1D], J[NO2] and J[HCHO]) in the four seasons range between −3.47% and −6.18% after turning off the BC absorption, which further leads to relative changes from −4.27% to −6.82%, −2.14% to −4.40% and −0.47% to −2.73% in hydroxyl (OH) radicals, hydroperoxyl (HO2) radicals and ozone (O3), respectively. However, different from the relative changes, the absolute changes in OH and HO2 radicals and O3 after turning off BC absorption show discrepancies among the different seasons. In the North China Plain (NCP) region, O3 concentration decreases by 1.79 ppb in the summer, which is higher than the magnitudes of 0.24–0.88 ppb in the other seasons. In southern China, the concentrations of OH and HO2 radicals reach the maximum decreases in the spring and autumn, followed by those in the summer and winter, which is due to the enhancement of solar radiation and the summer monsoon. Thus, BC inhibits the formation of atmospheric oxidants, which further weakens the atmospheric oxidative capacity.

Ultralean Combustion Mechanism of Methane–Air Swirling Premixed Flame

ABSTRACT This study investigated a methane – air premixed flame in a partially tapered swirl burner. Experimentally, we succeeded in forming almost steady ultralean flames with an equivalence ratio as lean as 0.465. On the other hand, a numerical simulation of the flame with detailed chemistry revealed that the flame head existed in a large recirculation zone under ultralean conditions. In addition, high-value peaks of temperature, heat-release rate (HRR), and concentrations of OH, O, and H radicals were formed at the flame head, enabling ultralean combustion. Subsequently, to identify the formation mechanism of these peaks, adiabatic swirl burner flames were simulated with and without the effect of thermal-diffusive imbalance (a Lewis number effect). The results show that a Lewis number of less than unity caused a temperature increase in the flame located in the recirculation zone owing to the thermal-diffusive imbalance, which increased the peak heights of the HRR and the three radicals. The results also showed that even in a flame unaffected by thermal-diffusive imbalance, the backward convective transport could accumulate CO and OH at the flame head thus enhancing the chemical reactions at the head. (185 words)

Characterization of sugar maple and red oak bark: Efficient lignin extraction via the Organosolv and acidic dioxane process

The barks of two wood species, sugar maple (SM) and red oak (RO), were investigated to characterize their chemical composition and isolate the lignins they contain, representing relatively underexplored and underutilized polymers. Characterizing these two barks involved assessing extractive components, Klason and acid-soluble lignin, ash content, and sugars. It was observed that RO bark had a higher concentration of extractive substances and a lower Klason lignin content compared to SM bark. The Klason lignin content in the barks of the SM and RO bark was measured at 35.0% and 26.4%, respectively, higher than values reported for corresponding to wood of the same species, 21.8% and 22.2%, respectively, for RO and SM. Lignin isolation from bark was achieved by utilizing Organosolv catalytic and acid dioxane processes. Notably, the Organosolv process yielded lignins of considerably higher purity. The structural analysis of the bark lignins was peformed by combination of spectroscopic methods: FTIR,13P NMR, and solid-state NMR. Compared to dioxane lignins, a higher concentration of OH bound to syringyl and guayacyl units were found in Organosolv lignins. In contrast, aliphatic OH units are more important in dioxane lignins than in Organosolv lignins. Furthermore, sugar analysis was conducted via HPLC, thermal analysis was conducted through DSC and TGA, and ash composition identification was done using ICP-OES. Notably, higher Mw and Mn values are determined by GPC for dioxane lignins than for Organosolv lignins.

Passivation and depassivation of reinforcement steel in alkali-activated materials—A review

This paper reviews the formation and breakdown of passive film on the surface of reinforcement steel in alkali-activated materials (AAMs) considering the characteristics of reaction product and pore solution chemistry. The literature review shows that the pore solution of AAMs has higher concentrations of OH−, Na+, silica and aluminium compared to Portland cement (PC). This relatively high alkalinity contributes to the generation of a passive film, which has positive effects on the corrosion resistance of reinforcement steel embedded in AAMs. The silica-aluminium zeolite layer present on the surface of passive film adsorbs chloride ions and effectively inhibits chloride-induced depassivation. Generally, lower ratios of [Cl−]/[SO42−] and [Cl−]/[S2O32−] potentially inhibit the depassivation of reinforcement steel. The high pH value and the elevated concentrations of HS− of AAMs contribute to the increase of critical chloride content (Ccrit). However, the higher content of reduced sulfide mainly dissolved from slag results in the consumption of dissolved oxygen, which is necessary for the formation of passive film. Generally, the presence of reduced sulfide forms Fe-S complexes on the surface of reinforcement steel in AAMs. Even so, higher corrosion resistance for AAMs is mostly expected with longer depassivation time due to finer microstructure and lower chloride penetration rates compared to PC-based materials. The decrease in pH value in the pore solution of the AAMs is the main factor affecting carbonation-induced depassivation of reinforcement steel, while high concentrations of bicarbonate and carbonate ions inhibit depassivation.

Experimental and reaction mechanism study on laminar burning velocity and characteristics of OH/NH generation in ammonia co-combustion

Developing fuels without carbon, such as ammonia (NH3), is crucial for achieving carbon reduction. Laminar burning velocity (LBV) is investigated, and distribution characteristics of OH and NH radicals are identified through planar laser-induced fluorescence. Rate of production of main free radicals and sensitivity analysis are also studied. The addition of NH3 to CH4-air mixtures results in a decrease in the LBV, a rise in preheating zone height, a reduction in OH radical fluorescence intensity, and an enhancement in NH radical fluorescence intensity. Simulation reveals that the high NH3 ratio enhance the negative impact of nitrogen-containing elementary reactions on LBV. The addition of NH3 enhances the initial consumption of more OH via reaction R248:NH2+OH=NH+H2O, leading to increased NH production, and indicating a negative effect on LBV. The decrease in OH concentration is the main factor leading to a decrease in LBV. The reactions affecting the OH generation and consumption are R39:H+O2=O+OH and R85:OH+H2=H+H2O, respectively. The addition of NH3 leads to a more significant reduction in R39.

The Discussion of Ignition Criterion About the Mechanical Spark Ignition of Near-Limit Methane-Air Mixtures.

An optimal ignition criterion must be selected for the numerical prediction of the ignition parameters for mechanical spark ignition of near-limit methane-air fuel mixtures based on fuel mixture equivalency ratio; wherein, the vast majority of ignition criteria can be used for stoichiometric fuel mixtures. However, the viability of each criterion must be individually determined for near-limit fuel mixtures. This study developed a high-resolution algorithm that can be used to model the mechanical spark ignition and combustion of methane-air fuel mixtures of varying equivalence ratios. Three ignition criteria, Van't Hoff, reaction heat release rate, and -OH concentration, were evaluated at varying equivalence ratios based on their respective distributions at varying times. The widely used Van't Hoff criterion cannot be used to predict near-limit fuel mixtures due to a high required ignition temperature and low rates of combustion. -OH concentration criterion is significantly affected by the rate of combustion and reaction temperature; therefore, it tends to erroneously overestimate ignition parameters for near-limit fuel mixtures. This study has found that reaction heat release rate criterion can be used at all equivalence ratios and faithfully produces ignition parameter trends for fuel mixture reaction schemes of varying simplifications. Reaction heat release rate is a valid ignition criterion because the location of peaks in reaction released heat at varying times corresponds to flame front location, which is its physical counterpart.

Structure-activity relationship, adsorption, and fenton-like catalytic oxidation capacity of iron-oxide nano-confined materials

In this study, iron-oxide was loaded into polystyrene macroporous microspheres containing sulfonate groups to prepare an environmental purification material with adsorption and Fenton-like oxidizing abilities. Iron-oxide is prone to inactivation due to reunion in the process of preparation and application, and this modification aimed to mitigate this problem. Subsequently, based on the microscopic characterization results and the effect on the treatment of methylene blue (MB) simulated wastewater, the structure-activity relationship of two key (OH− concentrations in precipitation solution and iron ion compositions in the impregnation solution) factors with the adsorption and catalytic oxidation ability of the iron-oxide nano-confined materials were explored. The results indicated that the samples both exhibited adsorption and catalytic oxidation capabilities. The removal efficiency of MB simulated wastewater can reached 95.3% after adsorption for 9 h, reaching 99.98% after catalytic oxidation for 6 h. In addition, the removal efficiency of the MB simulated wastewater exceeded 95% after 6 cycles. The concentration of OH− in precipitation solution could affect the volume of iron crystals on the carrier which affected the pore size of the sample and the adsorption capacity. It also influenced whether iron ions could be stably loaded inside the carrier, determining the conducting homogeneous or heterogeneous Fenton-like reactions and the stability of the samples. The composition of iron ions in the impregnating solution regulated the volume of the crystals and adsorption sites, which influenced the adsorption ability of the samples. In addition, the presence of Fe2+ could promote the progress of Fenton-like reactions. The identification results of the ROSs showed that •OH was the main free radical. The quenching experiment results showed that the contribution rate of •OH toward MB degradation reached 99.81%. In addition, the possible degradation pathways of MB were analyzed.

Inverse modeling of 2010–2022 satellite observations shows that inundation of the wet tropics drove the 2020–2022 methane surge

Atmospheric methane concentrations rose rapidly over the past decade and surged in 2020-2022 but the causes have been unclear. We find from inverse analysis of GOSAT satellite observations that emissions from the wet tropics drove the 2010-2019 increase and the subsequent 2020-2022 surge, while emissions from northern mid-latitudes decreased. The 2020-2022 surge is principally contributed by emissions in Equatorial Asia (43%) and Africa (30%). Wetlands are the major drivers of the 2020-2022 emission increases in Africa and Equatorial Asia because of tropical inundation associated with La Niña conditions, consistent with trends in the GRACE terrestrial water storage data. In contrast, emissions from major anthropogenic emitters such as the United States, Russia, and China are relatively flat over 2010-2022. Concentrations of tropospheric OH (the main methane sink) show no long-term trend over 2010-2022 but a decrease over 2020-2022 that contributed to the methane surge.

Novel insights into photoaging mechanisms and environmental persistence risks of polylactic acid (PLA) microplastics: Direct and indirect photolysis

Polylactic acid (PLA), as a biodegradable plastic, exhibits high sensitivity to ultraviolet (UV) radiation, yet the mechanisms and environmental risks of its photoaging remain unclear. This study uses quantum chemical calculations (DFT and TD-DFT) and kinetic simulations to explore the direct and indirect photoaging of PLA. Direct photoaging indicates that the highest oscillator intensity absorption peaks occurred at 172 and 246 nm, corresponding to the 13th singlet (S13) and 48th triplet (T48) states, thereby initiating the Norrish I and Norrish II mechanisms. The innovative “electron-hole” technology effectively clarifies the variations in photoaging mechanisms under different wavelengths. Indirect photoaging involves multiple reactive oxygen species (ROS) like •OH, 1O2, •O2−, and •HO2. The study confirms the anhydride production hypothesis and proposes two novel •OH-induced mechanisms: carbonyl carbon addition and branched methyl hydrogen dehydrogenation. Both mechanisms are thermodynamically advantageous, but their products pose potential environmental risks. ROS species and concentrations impact both PLA's photoaging mechanisms and environmental persistence. Low •OH concentration in northeast China, especially in winter, suggests a significant photoaging risk. This study offers pioneering insights into photoaging mechanisms and emphasizes the pivotal role of ROS, offering recommendations for managing PLA environmental impacts and fates in China.

Magnetically Enhanced Oxygen Evolution Reaction in Mild Alkaline Electrolytes by Building Catalysts on Magnetic Frame.

Under large current densities, the excessive hydroxide ion (OH) consumption hampers alkaline water splitting involving the oxygen evolution reaction (OER). High OH concentration (≈30wt.%) is often used to enhance the catalytic activity of OER, but it also leads to higher corrosion in practical systems. To achieve higher catalytic activity in low OH concentration, catalysts on magnetic frame (CMF) are built to utilize the local magnetic convection induced from the host frame's magnetic field distributions. This way, a higher reaction rate can be achieved in relatively lower OH concentrations. A CMF model system with catalytically active CoFeOx nanograins grown on the magnetic Ni foam is demonstrated. The OER current of CoFeOx@NF receives ≈90% enhancement under 400mT (900mAcm-2 at 1.65V) compared to that in zero field, and exhibits remarkable durability over 120h. As a demonstration, the water-splitting performance sees a maximum 45% magnetic enhancement under 400mT in 1m KOH (700mAcm-2 at 2.4V), equivalent to the concentration enhancement of the same electrode in a more corrosive 2m KOH electrolyte. Therefore, the catalyst-on-magnetic-frame strategy can make efficient use of the catalysts and achieve higher catalytic activity in low OH concentration by harvesting local magnetic convection.

Anode‐Electrolyte Interfacial Acidity Regulation Enhances Electrocatalytic Performances of Alcohol Oxidations

AbstractThe local acidity at the anode surface during electrolysis is apparently stronger than that in bulk electrolyte due to the deprotonation from the reactant, which leads to the deteriorated electrocatalytic performances and product distributions. Here, an anode‐electrolyte interfacial acidity regulation strategy has been proposed to inhibit local acidification at the surface of anode and enhance the electrocatalytic activity and selectivity of anodic reactions. As a proof of the concept, CeO2‐x Lewis acid component has been employed as a supporter to load Au nanoparticles to accelerate the diffusion and enrichment of OH− toward the anode surface, so as to accelerate the electrocatalytic alcohol oxidation reaction. As the result, Au/CeO2‐x exhibits much enhanced lactic acid selectivity of 81 % and electrochemical activity of 693 mA⋅cm−2 current density in glycerol oxidation reaction compared to pure Au. Mechanism investigation reveals that the introduced Lewis acid promotes the mass transport and concentration of OH− on the anode surface, thus promoting the generation of lactic acid through the simultaneous enhancements of Faradaic and non‐Faradaic processes. Attractively, the proposed strategy can be used for the electro‐oxidation performance enhancements of a variety of alcohols, which thereby provides a new perspective for efficient alcohol electro‐oxidations and the corresponding electrocatalyst design.

Anode-Electrolyte Interfacial Acidity Regulation Enhances Electrocatalytic Performances of Alcohol Oxidations.

The local acidity at the anode surface during electrolysis is apparently stronger than that in bulk electrolyte due to the deprotonation from the reactant, which leads to the deteriorated electrocatalytic performances and product distributions. Here, an anode-electrolyte interfacial acidity regulation strategy has been proposed to inhibit local acidification at the surface of anode and enhance the electrocatalytic activity and selectivity of anodic reactions. As a proof of the concept, CeO2-x Lewis acid component has been employed as a supporter to load Au nanoparticles to accelerate the diffusion and enrichment of OH- toward the anode surface, so as to accelerate the electrocatalytic alcohol oxidation reaction. As the result, Au/CeO2-x exhibits much enhanced lactic acid selectivity of 81 % and electrochemical activity of 693 mA⋅cm-2 current density in glycerol oxidation reaction compared to pure Au. Mechanism investigation reveals that the introduced Lewis acid promotes the mass transport and concentration of OH- on the anode surface, thus promoting the generation of lactic acid through the simultaneous enhancements of Faradaic and non-Faradaic processes. Attractively, the proposed strategy can be used for the electro-oxidation performance enhancements of a variety of alcohols, which thereby provides a new perspective for efficient alcohol electro-oxidations and the corresponding electrocatalyst design.

Abiotic chlorination of organic matter in the soil environment: A simulation study

Chlorination of organic matter occurs naturally and is an important part of the chlorine cycle. To investigate the likelihood that inorganic oxidants, (Fe(NO3)3, H2O2, and hydroxyl radicals (·OH), frequently present in soil environments, could promote the synthesis of chlorinated organic matter in the soil environment, litterfall, humus, and soil (0–20 cm) were collected and used in laboratory based simulation experiments. Results indicate that these inorganic oxidants might promote the synthesis of chlorinated organic matter, but their impact varied due to varying suitable reaction circumstances. Litterfall was the most sensitive to chlorination, likely caused by the presence of abundant amounts of labile organic matter, and the chlorination process was limited by its Cl− level. Hydroxyl radicals showed a dual effect (producing or degrading chlorinated organic matter) on the three materials assessed, which was controlled by both ·OH concentration and the stability of organic matter, and the dual effect was evident in order of litterfall > humus > soil. The Fe(NO3)3-mediated chlorination of organic matter was only significant in litterfall due to its labile organic matter composition, while the peroxidative reaction caused by H2O2 in the producing chlorinated organic matter was only obvious in soil, most likely due to the presence of metals, facilitating the process. Combined this study sheds light on the chlorine cycle by verifying that inorganic oxidants might mediate abiotic chlorination of organic matter in a natural soil environment.

Enhancing the production of reactive oxygen species in the rhizosphere to promote contaminants degradation in sediments by electrically strengthening microbial extracellular electron transfer

The production of reactive oxygen species (ROS) in the rhizosphere is limited by the low extracellular electron transfer capacity of indigenous microorganisms. In the present study, electrical stimulation was used to promote the generation of rhizospheric ROS by accelerating extracellular electron transfer. The result showed that •OH concentrations in the electrically stimulated group (ES group) exceeded the control group by 15.76 %. Accordingly, the removal rate of the target pollutant (i.e., 2,4-dichlorophenol, and sulfamethoxazole) was 20.01 %−24.80 % higher in the ES group than in the control group. The sediment of the ES group had a higher capacity (30.55 %) and a lower electrical resistance (29.15 %) compared to the control group, which subsequently promoted the dissimilatory iron reduction to produce Fe(II) for triggering a Fenton-like process. The increased extracellular respiratory capacity under electrical stimulation could be attributed to the polarization of C-N and CO bonds, which provided more electron storage sites and thus participated in proton-coupled electron transfer. In addition, the concentration of ATP and co-enzymes (NADH/NAD+ and Complex I/Complex III), reflecting electron exchange within respiratory chains, increased distinctly under electrical stimulation. Applying electrical stimulation seemed feasible to increase ROS production and contaminant degradation in the rhizosphere, deepening the understanding of electrical stimulation to promote the production of ROS in the natural system.

Continuous flow-through electro-Fenton membrane reactor with Fe−N4-doped carbon membrane as cathode for efficient removal of dimethylacetamide

Fe − N4-doped conductive carbon membranes (FeCMs) were fabricated through high-temperature carbonization using chitosan and phenolic resin as the raw materials and ammonium ferrous sulfate (NH4Fe(SO4)2) as the dopant. The impact of the NH4Fe(SO4)2 doping rate (0 − 15 wt%) on the structure and performance of the FeCM was investigated. Moreover, a continuous flow-through electro-Fenton membrane reactor (EFMR) was constructed using an FeCM cathode and a Ti plate anode for the efficient removal of dimethylacetamide (DMAC). The resultant carbon membrane with 10 wt% NH4Fe(SO4)2 (M10) exhibited a smaller pore size (40.1 nm), a higher porosity (48.3 %), a larger specific surface area (531.6 m2/g), and a higher mechanical strength (6.7 M Pa) than the other membranes. The removal rate of DMAC by EFMR with M10 as the cathode at 2 V reached 42.1 %, which was much greater than that without NH4Fe(SO4)2 (3.6 %). The electrosynthesis ·OH concentration by EFMR with M10 as the cathode was approximately 89.1 mg/L, which was much greater than that of most carbon-based materials. The intermediates of DMAC degradation (such as N-methylacetamide, acetamide, acetaldehyde, and acetic acid) were determined by gas chromatography–mass spectrometry (GC–MS), and the removal of total organic carbon (TOC) was approximately 3.4 %. Density functional theory (DFT) calculations revealed that the Fe atom served as the active site for dissolved oxygen adsorption and electrogeneration of ·OH. After 5 days of continuous EFMR operation, the DMAC removal rate remained at 88.8 % of the initial value (42.1 %). This study presents a novel approach for designing and fabricating conductive carbon membranes to improve industrial wastewater treatment performance.

Hydroxide-Source-Dependent Polymorphism and Phase Stability of Cobalt(II) Hydroxides in Diffusion-Driven Systems.

Hydroxides of cobalt(II) exist predominantly in two polymorphic forms, namely, the blue-green α-form [α-Co(OH)2] and reddish β-form [β-Co(OH)2]. These hydroxides have a layered structure with interlayer galleries of around 7 and 4 Å, respectively, for α- and β-Co(OH)2. In most of the previous studies, both the polymorphs were synthesized separately, and a few of them showed that the α-form gets converted to a thermodynamically more stable β-form via physical processes. In the present work, we have optimized the conditions for the simultaneous synthesis of both polymorphs under identical conditions in the same reactor using the 1D reaction-diffusion framework by employing different outer electrolytes. We found that the polymorph chemistry of Co(OH)2 depends on the source and concentration of OH- rather than other reaction conditions or later physical transformation. The products are characterized to confirm their morphology, structure, and chemical environment. We observed that the use of NaOH and NH4OH as the OH- precursor leads to α-Co(OH)2 only; however, with NaOH, a continuous precipitate is formed, and with NH4OH, periodic precipitation is formed. On the other hand, with hydrazine (HYZ) as the OH- source, Liesegang bands of α-Co(OH)2 and β-Co(OH)2 as granules are formed throughout the diffusion reactor. Another intriguing observation on the HYZ system is that at its high concentration, the bands of α-Co(OH)2 get converted to β-Co(OH)2. We articulate the reasons and mechanism of those observations.

Stability of Hydroxylated α-Fe2O3(0001) Surfaces.

The stability of hydroxylated terminations of the 0001 surface of α-Fe2O3 (hematite) is investigated computationally using PBE + U calculations with dispersion corrections. Hydroxylated surfaces with low OH concentrations are found to be most stable in a range of the chemical potential of water of -0.95 eV > μH2O > -2.22 eV. These surfaces can be described as isolated Fe(OH)3 groups adsorbed on the dry hematite surface and are predicted to be the exposed termination of the 0001 surface in a wide range of relevant experimental conditions. Most investigated reduced surfaces, containing Fe in oxidation state +2, are only stable in a range of the chemical potential of oxygen μO < -2.44 eV, where bulk hematite is less than magnetite. The only reduced surface stable at a higher μO is derived from the most stable nonreduced hydroxylated surfaces by removing a single OH group per unit cell.