H2 uptake and synthesis of the fluorinated Li-dispersed nickel oxide nanotubes

Aligned Li-dispersed nickel oxide nanotubes were prepared using LiNO₃, Ni(NO₃)₂·6H₂O and an anodic aluminum oxide (AAO) template for potential applications in H₂ storage. The nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The nickel(II) oxide nanotubes obtained had a trigonal structure with a uniform length, 40–50 nm in wall thickness and 200 ± 10 nm in the outer diameter. The external surface of the nanotubes was modified by fluorination. The level of H₂ adsorption was determined using the gravimetric method. The fluorinated Li-dispersed nickel oxide nanotubes showed a 0.06 wt% and 1.65 wt% increase in weight due to H₂ adsorption under an equilibrium pressure of 47 atm at 298 K and 77 K, respectively.     

Synthesis of a novel super-microporous layered material and its catalytic application in the vapor-phase Beckmann rearrangement of cyclohexanone oxime

A novel well-ordered super-microporous layered material, silica-pillared niobic acid, was synthesized by a guest-exchange route and structurally characterized by powder X-ray diffraction (XRD), infrared absorption spectroscopy (IR), thermogravimetric and differential thermal analysis (TG/DTA), transmission electron micrographs (TEM), nitrogen adsorption method and ammonia-temperature-programmed desorption (NH₃-TPD). The obtained silica-pillared layered niobic acid had a supergallery of 1.78 nm, a large BET surface area of 250 m² g⁻¹, and a high thermal stability exceeding 973 K.The pillared layered material was also found to be an efficient solid acid catalyst for the vapor-phase Beckmann rearrangement of cyclohexanone oxime. When 1-hexanol was fed with cyclohexanone oxime, this solid catalyst exhibited a 100% conversion of the oxime with a selectivity of ε-caprolactam beyond 85% at a reaction temperature of 613 K and a WHSV of 0.17 h⁻¹ in terms of cyclohexanone oxime, and there was no significant change of the conversion and selectivity within 6 h.     

Mesoporous hybrid zirconium oxophenylphosphate synthesized in absence of any structure directing agent

A new organic–inorganic hybrid mesoporous zirconium oxophenylphosphate (ZPP-1) has been synthesized hydrothermally at 443 K by using phenylphosphonic acid (PPA) as phosphorus source in absence of any structure directing agent. Powder XRD, TEM, FE SEM, N₂ sorption, CHN and ICP-AES chemical analyses, ¹³C CP/MAS and ³¹P MAS NMR, UV–visible and FT IR spectroscopic tools and thermal analysis were employed to characterize this novel material. XRD, N₂ sorption and TEM image analysis suggested the existence of multi-lamellar structure of the pore wall with large micropores and mesopores having peak maximums of ca. 1.5 and 5.0–6.0 nm, respectively in this ZPP-1 material. Interestingly, this hybrid material showed very high thermal stability together with retention of nanostructure and phenyl group when heated upto 723 K. ZPP-1 showed fairly high H₂ adsorption capacity under atmospheric pressure at 77 K. Possible templating role played by the framework phenyl groups has been discussed.     

Simultaneous removal of 3d transition metals from multi-component solutions by activated carbons from co-mingled wastes

The main purpose of the present work was to study the simultaneous removal of 3d transition metals from multi-component solutions by novel porous material obtained from carbon-containing liquid and solid waste. The activated carbon was prepared from co-mingled natural organic waste: 25% sunflower husks, 50% petroleum waste and 25% low-grade bituminous coal. The porous carbon material was obtained via stages of pre-oxidation with binary eutectic Na/K carbonates (in order to avoid melting and coke formation), followed by “step by step” carbonization at 100–400 °C in an inert atmosphere and activation with steam at 850 °C.

The adsorption of the 3d transition metals: copper (II), cobalt (III), nickel (II), iron (III), and chromium (III), on novel activated carbons has been investigated using multi-component model solutions. Experiments have been carried out on the thermodynamics of the simultaneous adsorption of the 3d transition metals in a static mode. The total metal removal combines the process of metal hydroxide precipitation in the solution with the metal cation adsorption on negatively charged carbon surface in a single operation unit. The carbon/metals interaction at the surface of spent adsorbents is discussed.     

The effect of the Rh–Al, Pt–Al and Pt–Rh–Al surface alloys on NO conversion to N2 on alumina supported Rh, Pt and Pt–Rh catalysts

NO conversion to N₂ in the presence of methane and oxygen over 0.03 at.%Rh/Al₂O₃, 0.51 at.%Pt/Al₂O₃ and 0.34 at.%Pt–0.03 at.%Rh/Al₂O₃ catalysts was investigated.

δ-Alumina and precious metal–aluminum alloy phases were revealed by XRD and HRTEM in the catalysts.

The results of the catalytic activity investigations, with temperature-programmed as well as steady-state methods, showed that NO decomposition occurs at a reasonable rate on the alloy surfaces at temperatures up to 623 K whereas some CH₄ deNO_x takes place on δ-alumina above this temperature. A mechanism for the NO decomposition is proposed herein. It is based on NO adsorption on the precious metal atoms followed by the transfer of electrons from alloy to antibonding π orbitals of NO_(ads.) molecules. The CH₄ deNO_x was shown to occur according to an earlier proposed mechanism, via methane oxidation by NO_2(ads.) to oxygenates and then NO reduction by oxygenates to N₂.     

Adsorption of acid orange 7 dye in aqueous solutions by spent brewery grains

Spent brewery grains (SBG), a by-product of the brewing process, were tested as an adsorbent of acid orange 7 dye (AO7), a monoazo acid dye currently used in paper and textile industries. The presence of AO7 in these effluents causes obvious environmental problems.

Kinetics studies of adsorption of AO₇ to SBG (3.75%, m/v) were carried out at 20 °C, using aqueous solutions with different AO7 concentrations (30–834 mg/L). For every situations tested, no significant variation in residual AO7 concentration in solution was detected after 1 h contact between the dye and the adsorbent. The adsorption process followed a pseudo-first order model.

The equilibrium process showed to be well described by both Freundlich and Langmuir isotherm models, at 20 and 30 °C. The maximum adsorption capacity was estimated to be 30.5 mg AO7/g SBG, at 30 °C.

Free energy of adsorption (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were calculated to predict the nature of adsorption. The estimated values for ΔG° were −22.78 and −24.53 kJ/mol, respectively, at 293.3 K (20 °C) and 303.3 K (30 °C), which are rather low indicating that a spontaneous process occurred. The enthalpy changes and entropy of adsorption were 28.66 and 175.36 J/mol K, respectively. The positive value for ΔH° indicates that the adsorption of AO7 dye to SBG is an endothermic process. The positive value of entropy reflects the affinity of the adsorbent for AO7 dye.

The obtained results are very promising since: (i) high levels of colour removal (>90%) were achieved with low contact times adsorbent/dye (less than 1 h contact); and (ii) the whole SBG can be successfully used as adsorbent of AO7 dye in aqueous solution without needing any previous treatments such as milling and/or sieving. Spent grains, being a cheap, and easily available material, can be an alternative for more costly adsorbents used for dye removal in wastewater treatment processes.     

CO oxidation and oxygen-assisted CO adsorption/desorption on Ag/MnOx catalysts

A series of Ag-doped manganese oxide catalyst were synthesized by the reflux method in an acid medium. The surface structure of the catalysts was characterized by N₂ adsorption, XRD and TEM experiments. The catalysts showed excellent catalytic activity for CO oxidation. The adsorption and oxidation of CO on a 1.0% Ag/MnO_x catalyst between 393 and 493 K were studied by means of single pulse experiments in a TAP reactor. The adsorption of CO was reversible at these temperatures and CO₂ was formed in an oxidation reaction of CO and lattice oxygen. Curve fitting to the experimental TAP response curves of the reactant and product was used to determine the kinetic parameters for the elementary steps. The activation energies were 83 kJ/mol for CO desorption, 31 kJ/mol for CO₂ desorption, and 116 kJ/mol for the surface CO oxidation by lattice oxygen. In addition, the effect of coadsorbed O₂ on CO adsorption was studied by the TAP technique. Below 353 K, there was a sharp increase, by about one order of magnitude, in the rate constant of CO adsorption promoted by the presence of coadsorbed O₂.     

H2S adsorption on polycrystalline UO2

We report results on the adsorption and desorption of H₂S on polycrystalline UO₂ at 100 and 300 K, using ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), low energy ion scattering (LEIS), and temperature programmed desorption (TPD). Our work is motivated by the potential for using the large stockpiles of depleted uranium in industrial applications, e.g., in catalytic processes, such as hydrodesulfurization (HDS) of petroleum. H₂S is found to adsorb molecularly at 100 K on the polycrystalline surface, and desorption of molecular H₂S occurs at a peak temperature of 140 K in TPD. Adsorption rates of sulfur as a function of H₂S exposure are measured using XPS at 100 K; the S 2p intensity and lineshapes demonstrate that the saturation coverage of S-containing species is 1 monolayer (ML) at 100 K, and is 0.3–0.4 ML of dissociation fragments at 300 K. LEIS measurements of adsorption rates agree with XPS measurements. Atomic S is found to be stable to >500 K on the oxide surface, and desorbs at 580 K. Evidence for a recombination reaction of dissociative S species is also observed. We suggest that O-vacancies, defects, and surface termination atoms in the oxide surface are of importance in the adsorption and decomposition of S-containing molecules.     

Conversion of N2O to N2 on TiO2(1 1 0)

In this study, we examine the interaction of N₂O with TiO₂(1 1 0) in an effort to better understand the conversion of NO_x species to N₂ over TiO₂-based catalysts. The TiO₂(1 1 0) surface was chosen as a model system because this material is commonly used as a support and because oxygen vacancies on this surface are perhaps the best available models for the role of electronic defects in catalysis. Annealing TiO₂(1 1 0) in vacuum at high temperature (above about 800 K) generates oxygen vacancy sites that are associated with reduced surface cations (Ti³⁺ sites) and that are easily quantified using temperature programmed desorption (TPD) of water. Using TPD, X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS), we found that the majority of N₂O molecules adsorbed at 90 K on TiO₂(1 1 0) are weakly held and desorb from the surface at 130 K. However, a small fraction of the N₂O molecules exposed to TiO₂(1 1 0) at 90 K decompose to N₂ via one of two channels, both of which are vacancy-mediated. One channel occurs at 90 K, and results in N₂ ejection from the surface and vacancy oxidation. We propose that this channel involves N₂O molecules bound at vacancies with the O-end of the molecule in the vacancy. The second channel results from an adsorbed state of N₂O that decomposes at 170 K to liberate N₂ in the gas phase and deposit oxygen adatoms at non-defect Ti⁴⁺ sites. The presence of these O adatoms is clearly evident in subsequent water TPD measurements. We propose that this channel involves N₂O molecules that are bound at vacancies with the N-end of the molecule in the vacancy, which permits the O-end of the molecule to interact with an adjacent Ti⁴⁺ site. The partitioning between these two channels is roughly 1:1 for adsorption at 90 K, but neither is observed to occur for moderate N₂O exposures at temperatures above 200 K. EELS data indicate that vacancies readily transfer charge to N₂O at 90 K, and this charge transfer facilitates N₂O decomposition. Based on these results, it appears that the decomposition of N₂O to N₂ requires trapping of the molecule at vacancies and that the lifetime of the N₂O–vacancy interaction may be key to the conversion of N₂O to N₂.     

SAPO-34 membranes for CO2/CH4 separations: Effect of Si/Al ratio

Silicoaluminophosphate (SAPO) membranes with Si/Al gel ratios from 0.05 to 0.3 were synthesized by in situ crystallization onto porous, tubular stainless steel support. Pure SAPO-34 membranes were obtained when the Si/Al ratio was 0.15 or higher. The adsorbate polarizability correlated with the adsorption capacity on SAPO-34, and the amounts of gases adsorbed were in the order: CO₂ > CH₄ > N₂ > H₂. The Si/Al ratio did not affect the pore volume significantly, but it changed the CO₂ and CH₄ adsorption equilibrium constants. The SAPO-34 membranes effectively separated CO₂ from CH₄ for feed pressures up to 7 MPa. At 295 K, for a pressure drop of 138 kPa and a 50/50 feed, the CO₂/CH₄ selectivity was 170 for a membrane with a Si/Al gel ratio of 0.15. At 7 MPa, the CO₂/CH₄ selectivity was 100 and the CO₂ permeance was 4 × 10⁻⁸ mol/(m² · s · Pa) at 295 K. This membrane was also separated CO₂/N₂ (selectivity = 21) and H₂/CH₄ (selectivity = 32) mixtures at 295 K and a pressure drop of 138 kPa. Competitive adsorption and difference in diffusivities are responsible for CO₂/CH₄ and CO₂/N₂ separations, whereas the H₂/CH₄ separation was due to diffusivity differences. For a membrane with Si/Al gel ratio of 0.1, a mixture of SAPO-34 and SAPO-5 formed, and the CO₂/CH₄ selectivity was lower.     

Influence of the preparation method on the catalytic behaviour of PtSn/TiO2 catalysts

PtSn/TiO₂ catalysts containing 2 wt% Pt and a Pt:Sn atomic ratio of 2:1 and 1:1 were prepared by coimpregnation or successive impregnation method with aqueous solutions of SnCl₂·2H₂O and H₂PtCl₆·6H₂O of a commercial TiO₂ (P25, from Degussa). Both catalyst series, independent of the preparation method, were reduced at 473 and 773 K. XPS results show that tin was in an oxidized state after reduction at 473 K, and that a fraction was in the metallic state after reduction at 773 K. By use of in situ FTIR spectroscopy of adsorbed CO, the presence of bimetallic Pt–Sn phases was assessed after reduction at 773 K. Microcalorimetric analysis of CO adsorption enthalpy indicates that reduction at 773 K causes the appearance of a more heterogeneous distribution of active sites, as well as a loss in the amount of sites. The catalytic activity for the gas phase hydrogenation of crotonaldehyde was greatly improved when the catalysts were prepared by coimpregnation, at both reduction temperatures. The selectivity toward crotyl alcohol was higher after reduction at 773 K and independent of the preparation method, although it increased with the amount of tin, suggesting a promoting effect of tin on this reaction.     

Alkali and alkaline-earth cation exchanged chabazite zeolites for adsorption based CO2 capture

In this study chabazite zeolites were prepared and exchanged with alkali cations – Li, Na, K and alkaline-earth cations – Mg, Ca, Ba and were studied to assess their potential for CO₂ capture from flue gas by vacuum swing adsorption for temperatures below 120 °C. Isotherm measurements (CO₂ and N₂) were made for all samples at 273 K, 303 K and 333 K using a volumetric apparatus and represented with the Dual-site Langmuir model for CO₂ and N₂. Henry’s constants and isosteric heats of adsorption were calculated and qualitative analyses performed for all samples. Adiabatic separation factor (ASF) and capture figure of merit (CFM) were proposed and used as indices for assessing adsorbent performance and compared with a commercial NaX-zeolite sample. It was found that NaCHA and CaCHA hold comparative advantages for high temperature CO₂ separation whilst NaX shows superior performance at relatively low temperatures.     

Adsorption studies on the treatment of textile dyeing effluent by activated carbon prepared from olive stone by ZnCl2 activation

This study aimed to investigate the removal of a reactive dye from aqueous solution by adsorption. Activated carbon prepared from olive stone, an agricultural solid by-product, was used as adsorbent. Different amounts of activating agent (ZnCl₂) and adsorbent particle size were studied to optimise adsorbent surface area. The adsorption experiments were conducted at different process parameters such as adsorbent dose, temperature, equilibrium time and pH. The experimental results showed that at equilibrium time 120 min, optimum pH ranged between 3 and 4, and adsorbent dosage was 2.0 g 200 ml⁻¹. While the kinetic data support pseudo-second order, a pseudo-first order model shows very poor fit. Adsorption isotherms were obtained at three different temperatures (288, 298 and 308 K). The fitness of adsorption data to the Langmuir and Freundlich isotherms was investigated. In addition, the thermodynamic parameters such as isosteric enthalpy of adsorption (Δ H _ads) _y , isosteric entropy of adsorption (Δ S _ads) _y and free energy of adsorption Δ G ⁰_ads were calculated. BET surface area measurements were made to reveal the adsorptive characteristics of the produced active carbon. The surface area of the activated carbon produced with 20% w/w ZnCl₂ solution was 790.25 m² g⁻¹.     

Investigation of simultaneous adsorption of SO2 and NOx on Na-γ-alumina with transient techniques

The simultaneous adsorption of SO₂ and NO_x on Na-γ-alumina was studied by means of step experiments in a fixed bed plug flow reactor at 387 K and atmospheric pressure. Typically the molar composition of the feed gas was 1.5% SO₂, 1% O₂, 4000 ppm NO, 500 ppm NO₂, and Ar. First the adsorption behavior of the pure components was measured. SO₂ and NO₂ adsorb easily, whereas NO and O₂ do not adsorb. Moreover there is no influence of O₂ on the adsorption behavior of the pure components.

NO and O₂ adsorption require the simultaneous presence of SO₂, NO, and O₂. The NO and O₂ adsorption rate is enhanced by an increasing SO₂/NO ratio. The total amount of SO₂ adsorbed is not affected by the simultaneous adsorption of NO and O₂. However, NO₂ adsorption increases the SO₂ adsorption capacity. In the presence of NO₂ most of the adsorbed NO_x is released as NO.     

Integrated high temperature gas cleaning: Tar removal in biomass gasification with a catalytic filter

A nickel-based catalytic filter material for the use in integrated high temperature removal of tars and particles from biomass gasification gas was tested in a broad range of parameters allowing the identification of the operational region of such a filter. Small-scale porous alumina filter discs, loaded with approximately 2.5 wt% Al₂O₃, 1.0 wt% Ni and 0.5 wt% MgO were tested with a particle free synthetic gasification gas with 50 vol% N₂, 12 vol% CO, 10 vol% H₂, 11 vol% CO₂, 12 vol% H₂O, 5 vol% CH₄ and 0–200 ppm H₂S, and the selected model tar compounds: naphthalene and benzene. At a typical face velocity of 2.5 cm/s, in the presence of H₂S and at 900 °C, the conversion of naphthalene is almost complete and a 1000-fold reduction in tar content is obtained. Technically, it would be better to run the filter close to the exit temperature of the gasifier around 800–850 °C. At 850 °C, conversions of 99.0% could be achieved in typical conditions, but as expected, only 77% reduction in tars was achieved at 800 °C.

Conversion data can be reasonably well described with first order kinetics and a dominant adsorption inhibition of the Ni sites by H₂S. The apparent activation energies obtained are similar to those reported by other investigators: 177 kJ/mol for benzene and 92 kJ/mol for naphthalene. The estimated heat of adsorption of H₂S is 71 kJ/mol in the benzene experiments and 182 kJ/mol in the naphthalene experiments, which points at very strong adsorption of H₂S. Good operation of the present material can hence only be guaranteed at temperatures above 830 °C mainly due to the strong deactivation by H₂S at lower temperatures.     

Determination of relative acid strength and acid amount of solid acids by Ar adsorption

Relative acid strength and acid amount of solid acids (alumina, silica-alumina, sulfated zirconia, mordenite, ZSM-5, beta, Y, and reduced MoO₃) are determined by argon adsorption technique. To obtain the heat of Ar adsorption and saturated adsorption amount, the adsorption isotherm is analyzed using the theory reported by Cremer and Flügge. The obtained heats of Ar adsorption and saturated adsorption amounts of sulfated zirconia catalysts and proton-type zeolites correspond well with the activities of acid-catalyzed pentane isomerization of these catalysts. The heats of adsorption were −22 kJ mol⁻¹ for sulfated zirconia, and ca. −19 kJ mol⁻¹ for mordenite, ZSM-5, and beta. Molybdenum oxides reduced at 623 and 773 K show large heat of adsorption (−19.3 and −19.7 kJ mol⁻¹, respectively), and these are classified into the superacid.     

A regenerable Fe/AC desulfurizer for SO2 adsorption at low temperatures

A novel regenerable Fe/activated coke (AC) desulfurizer prepared by impregnation of Fe(NO₃)₃ on an activated coke was investigated. Experiment results showed that at 200 °C the SO₂ adsorption capacity of the Fe/AC was higher than that of AC or Fe₂O₃. Temperature-programmed desorption (TPD) revealed that H₂SO₄ and Fe₂(SO₄)₃ were generated on the desulfurizer upon adsorption of SO₂. Effect of desulfurization temperature was also investigated which revealed that with increasing temperature from 150 to 250 °C, the SO₂ removal ability gradually increases. The used Fe/AC can be regenerated by NH₃ at 350 °C to directly form solid ammonium-sulfate salts.     

Activity, selectivity and durability of VO–ZSM-5 catalysts for the selective catalytic reduction of NO by ammonia

ZSM-5 zeolite was loaded with vanadyl ions (VO²⁺) by treatment of Na–ZSM-5 with aqueous VOSO₄ solution at pH 1.5–2. The catalytic material was tested for the selective catalytic reduction of NO with ammonia at temperatures between 473 and 823 K and normal pressure using a feed of 1000 ppm NO, 1000 (or 1100) ppm NH₃ and 2% O₂ in He. The catalyst proved to be highly active, providing, e.g. initial NO conversions of >90% at 620 l g⁻¹ h⁻¹ (≈400 000 h⁻¹) and 723 K, and selective, providing nitrogen yields equal to NO conversion at equimolar feed in a wide temperature range and only minor N₂O formation at NH₃ excess. Admixture of SO₂ (200 ppm) resulted in an upward shift of the useful temperature range, but did not affect the catalytic behaviour at temperatures ≥623 K. No SO₂ conversion was noted at T ≤ 723 K and 450 l g⁻¹ h⁻¹. The poisoning effect of water (up to 4.5 vol%) was weak at temperatures between 623 and 773 K. VO-ZSM-5 catalysts are gradually deactivated already under dry conditions, probably by oxidation of the vanadyl ions into pentavalent V species. This deactivation is considerably accelerated in the presence of water.     

Activation of monolithic catalysts based on diatomaceous earth for sulfur dioxide oxidation

The formation of the active phases during the activation process of monolithic catalysts based on V₂O₅–K₂SO₄ supported on diatomaceous earth for SO₂ to SO₃ oxidation in flue gases, has been shown to be a crucial factor to achieve satisfactory catalytic performance. As the temperature is increased from room temperature to 470°C, SO₂ and SO₃ are taken up by the green catalyst and the precursors are transformed into the active species. The role of each component of the catalyst during the activation was analyzed by studying the behavior towards SO₂ adsorption of four materials, which contained: diatomaceous earth, diatomaceous earth + V, diatomaceous earth + K, and diatomaceous earth + V + K. The influence of the potassium sulfate accessibility in the green catalyst was studied by using two different preparation methods, which gave rise to differences in the catalysts SO₂ adsorption properties and catalytic performance. Furthermore, the influence of the activation atmosphere was studied using nitrogen, oxygen or a flue gas composition. It was shown that pyrosulfate species should be formed at temperatures below 400°C, to keep the vanadium in the active 5+ oxidation state.     

Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O

A multi-component NO_x-trap catalyst consisting of Pt and K supported on γ-Al₂O₃ was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H₂O and CO₂ on NO_x storage. The Al₂O₃ support was shown to have NO_x trapping capability with and without Pt present (at 250 °C Pt/Al₂O₃ adsorbs 2.3 μmols NO_x/m²). NO_x is primarily trapped on Al₂O₃ in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO_x/m², and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al₂O₃ catalyst are coordinated on the Al₂O₃ support at saturation.

When 5% CO₂ was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H₂O was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al₂O₃-based nitrates decreased by 92%. Interestingly, with both 5% CO₂ and 5% H₂O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al₂O₃ destabilized the K–CO₂ bond; specifically, H₂O mitigates the NO_x storage capacity losses associated with carboxylate competition.