Adsorption of NO and CO and specific features of their interaction on the Pt(100) surface

This article presents an analytical review of the author’s results and the literature concerning the nature of species resulting from NO and CO adsorption on the unreconstructed (1 × 1) and reconstructed hexagonal (hex) Pt(100) surfaces, including specific features of the reactions between these species. At 300 K, both surfaces adsorb NO and CO mainly in their molecular states. When adsorbed on Pt(100)-1 × 1, the NO_ads and CO_ads molecules are uniformly distributed on the surface. Under the same conditions, the hexagonal surface undergoes adsorption-induced reconstruction with the formation of NO_ads/1 × 1 and CO_ads/1 × 1 islands, which are areas of the unreconstructed phase saturated with adsorbed molecules and surrounded with the adsorbate-free hex phase. In adsorption on structurally heterogeneous surfaces containing both hex and 1 × 1 areas, the 1 × 1 and hex phases are occupied in succession, the latter undergoing reconstruction into the 1 × 1 phase. The reaction between NO and CO on the unreconstructed surfaces occurs even at room temperature and results in the formation of N₂ and CO₂ in quantitative yield. On the hexagonal surface, a stable layer of adsorbed molecules as (NO_ads + CO_ads)/1 × 1 mixed islands forms under these conditions. Above 350 K, the reaction in the mixed islands is initiated by the desorption of small amounts of the initial compounds, and this is followed by rapid self-acceleration leading to a surface explosion yielding N₂, CO₂, and N₂O (minor product). These products show themselves as very narrow desorption peaks in the temperature-programmed reaction spectrum.     

Promotion of Non-thermal Plasma on Catalytic Reduction of NOx by C3H8 Over Co/BEA Catalyst at Low Temperature

The effects of non-thermal plasma on selective catalytic reduction of NO_x by C₃H₈ (C₃H₈-SCR) over Co/BEA catalyst were investigated over a wide range of reaction temperatures (473–773 K). The significant synergistic effect between non-thermal plasma and catalytic reduction by C₃H₈ was exhibited at low temperatures from 473 to 673 K. The synergetic effect diminished with increasing temperature. The NO_x removal efficiency of non-thermal plasma facilitated C₃H₈-SCR hybrid system increased significantly with the increase in NO₂/NO ratio from 0.13 to 1.06 when the specific input energy increased from 0 to 136 J L^?1. The oxidation performance of NO to NO₂ was significantly enhanced by C₃H₈ in the plasma reactor. Results of CO₂/CO ratio and CO₂ selectivity suggested that adding non-thermal plasma improved CO₂ selectivity of C₃H₈-SCR. 200 ppm SO₂ slightly inhibited NO_x conversion of the non-thermal plasma facilitated C₃H₈-SCR hybrid system at below 673 K, whereas it exhibited no obvious effect at over 673 K. Non-thermal plasma was more selective toward NO oxidation than SO₂ oxidation in the presence of C₃H₈. The non-thermal plasma facilitated C₃H₈-SCR hybrid system could be used stably in durability tests with several hundreds ppm of SO₂.     

Structural and Magnetic Study of N2, NO,NO2, and SO2 Adsorbed within a Flexible Single‐Crystal Adsorbent of [Rh2(bza)4(pyz)]n

The crystalline one‐dimensional compound, [Rh^II₂(bza)₄(pyz)]_n ( 1 ) (bza=benzoate, pyz=pyrazine) demonstrates gas adsorbency for N₂, NO, NO₂, and SO₂. These gas‐inclusion crystal structures were characterized by single‐crystal X‐ray crystallography as 1 ?1.5 N₂ (298 K), 1 ?2.5 N₂ (90 K), and 1 ?1.95 NO (90 K) under forcible adsorption conditions and 1 ?2 NO₂ (90 K) and 1 ?3 SO₂ (90 K) under ambient pressure. Crystal‐phase transition to the P space group that correlates with gas adsorption was observed under N₂, NO, and SO₂ conditions. The C2/c space group was observed under NO₂ conditions without phase transition. All adsorbed gases were stabilized by the host lattice. In the N₂, NO, and SO₂ inclusion crystals at 90 K, short interatomic distances within van der Waals contacts were found among the neighboring guest molecules along the channel. The adsorbed NO molecules generated the trans‐NO???NO associated dimer with short intermolecular contacts but without the conventional chemical bond. The magnetic susceptibility of the NO inclusion crystal indicated antiferromagnetic interaction between the NO molecules and paramagnetism arising from the NO monomer. The NO₂ inclusion crystal structure revealed that the gas molecules were adsorbed in the crystal in dimeric form, N₂O₄.     

Mesoporous structures in never-dried softwood cellulose fibers investigated by nitrogen adsorption

Nitrogen adsorption was used to characterize mesoporous structures in never-dried softwood cellulose fibers. Distinct inflections in desorption isotherms were observed over the relative vapor pressure (P/P₀) range of 0.5–0.42 for never-dried cellulose fibers and partially delignified softwood powders. The reduction in N₂ adsorption volume was attributed to cavitation of condensed N₂ present in mesopores formed via lignin removal from wood cell walls during delignification. The specific surface areas of significantly delignified softwood powders were ~150 m² g^?1, indicating that in wood cell walls 16 individual cellulose microfibrils, each 3–4 nm in width, form one cellulose fibril bundle surrounded with a thin layer of lignin and hemicelluloses. Analysis of N₂ adsorption isotherms indicates that mesopores in the softwood cellulose fibers and partially delignified softwood powders had peaks ranging from 4 to 20 nm in diameter.     

Synthesis and characterization of small-mesopore-added silicalite-1 zeolites using single wall carbon nanohorn templating

Small-mesopore-added silicalite-1 zeolites were prepared by using single wall carbon nanohorn (SWCNH) as a template. The samples were characterized with X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy (TEM) and molecular probe adsorption methods. The pore size distributions determined with N₂ adsorption at 77 K showed the presence of small mesopores in 2–4 nm pore widths, in addition to their intrinsic micropores of 0.58 nm. The mesopore volume was 0.06 cm³ g^?1. The presence of small mesopores in the SWCNH-templated silicalite-1 zeolites was supported with TEM observation as well as the liquid phase adsorption of methylene blue, which was much higher than that on a bulk (purely microporous) silicalite-1.     

Adsorption and desorption behavior of tetravalent zirconium onto a silica-based macroporous TODGA adsorbent in HNO3 solution

To understand the separation behavior of Zr(IV) in the partitioning process for high level liquid waste, a silica-based macroporous adsorbent (TODGA/SiO₂-P) was prepared by impregnating N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) into a macroporous silica/polymer composite particles support (SiO₂-P). Adsorption and desorption behavior of Zr(IV) from nitric acid solution onto silica-based TODGA/SiO₂-P adsorbent were investigated by batch experiment. It was found that TODGA/SiO₂-P showed strong adsorption affinity to Zr(IV) and this adsorption process reached equilibrium state around 6 h at 298 K. Meanwhile, HNO₃ concentration had no significant effect on the adsorption of Zr(IV) above 1 M. From calculated thermodynamic parameters, this adsorption process could occur spontaneously at the given temperature and was confirmed to be an exothermic reaction. This adsorption process could be expressed by Langmuir monomolecular layer adsorption mode and the maximum adsorption capacity were determined to be 0.283 and 0.512 mmol/g for Zr(IV) at 298 and 323 K, respectively. In addition, more than 90 % of Zr(IV) adsorbed onto adsorbent could be desorbed with 0.01 M diethylenetriamine pentaacetic acid solution within 24 h at 298 K.     

Hydrocarbon Assisted NO Oxidation with Non-thermal Plasma in Simulated Marine Diesel Exhaust Gases

The NO oxidation performance in a non-thermal plasma (NTP) reactor under realistic synthetic exhaust gas compositions is investigated. The gas compositions differ mainly in the NO–NO₂ ratio and represent different modes of operation of a marine diesel engine. It is found that the maximum NO oxidation efficiency is independent on the NO–NO₂ ratio. Up to 55 % of the NO is mainly oxidised to NO₂ in all gas mixtures being analysed. However, the specific energy density needed to reach the highest NO oxidation varies with the gas composition between 15 and 60 J/L. The performance of the NTP-reactor was significantly improved by the addition of propene (C₃H₆) acting as an additional oxidising agent. The energy consumption for NO–NO₂ conversion was found to be between 20 and 45 eV/NO, depending on the ratio of the added propene as well as the initial concentrations of nitrogen oxides.     

Pilot-Scale Aftertreatment Using Nonthermal Plasma Reduction of Adsorbed NOx in Marine Diesel-Engine Exhaust Gas

Regulations governing marine diesel engine NO_x emissions have recently become more stringent. As it is difficult to fulfill these requirements by combustion improvements alone, effective aftertreatment technologies are needed to achieve efficient NO_x reductions. In this study, we develop an effective NO_x-reduction aftertreatment system for a marine diesel engine that employs combined nonthermal plasma (NTP) and adsorption. Compared with selective catalytic reduction, the proposed technology offers the advantages of not requiring a urea solution or harmful heavy-metal catalysts and low operating temperatures of less than 150 °C. The NO_x reduction comprises repeated adsorption and desorption flow processes using NTP combined with NO_x adsorbents made of MnO_x–CuO. High concentrations of NO_x are treated by NTP after NO_x adsorption and desorption, and this aftertreatment system demonstrates excellent energy efficiencies of 161 g(NO₂)/kWh, which fulfills the most recent International Maritime Organization emission NO_x standards in the Tier II–III regulations for 2016 and requires only 4.3 % of the engine output power.     

The uranium recovery from aqueous solutions using amidoxime modified cellulose derivatives. IV. Recovery of uranium by amidoximated hydroxypropyl methylcellulose

Amidoxime modified hydroxypropyl methylcellulose (HPMC) films (HPMC-g-AO) were used for the recovery of uranium from aqueous solutions by a complexation process. The adsorption experiments were carried out by immersion of a certain amount of films in UO₂ ²⁺ solutions (resultant pH 4.1) ranging in concentration from 100 to 1,000 ppm. The effect of temperature (25–50 °C) on the adsorption capacity of HPMC-g-AO was investigated at the optimized time. The adsorption kinetics and the thermodynamics as well as the adsorption capacity of HPMC-g-AO films were investigated. The adsorption capacity was found as 765 mg UO₂ ²⁺/g dry film. The kinetic and the thermodynamic parameters (i.e. activation energy, enthalpy, entropy and Gibbs free energy) for the interaction of UO₂ ²⁺ with HPMC-g-AO were calculated based on known basic relations. The results showed that adsorption occurred through strong electrostatic interactions with an enthalpy of ?36.5 kJ/mol. The desorption of UO₂ ²⁺ were investigated using different desorption agents such as EDTA, HCl, NaHCO₃, and NaOH. After the 2 weeks treatment period, the highest desorption yield were found as 23 % with NaHCO₃.     

Preparation of Silicates Using HSi(OC2H5)3 and Their NO x -Adsorption Behavior

The preparation and NO-adsorption/desorption behavior of Li, Ca and Ba silicates were investigated aiming at the application to a NO_x-absorbent. Li silicate was prepared by reaction of HSi(OC₂H₅)₃ with aqueous lithium silicate solution (LSS). Ca and Ba silicates were prepared from gels obtained using CH₃Si(OC₂H₅)₃, Si(OC₂H₅)₄, HSi(OC₂H₅)₃ and alkaline-earth alkoxides. The surface of these silicates indicated the solid basicity of H₀ = 9 and adsorbed the acidic gas of NO. FT-IR spectra of the silicates adsorbing NO showed the absorption peaks in the range of 1300–1600 cm^{– 1} corresponding to ionic and covalent nitrate NO₃^–. The complete desorption of adsorbed NO species occurred above 500°C in the Li silicate, above 500°C in the Ca and Ba silicates prepared using CH₃Si(OC₂H₅)₃, and above 700°C in the Ba and Ca silicates prepared using Si(OC₂H₅)₄. Regarding the Ca and Ba silicates, the difference in siloxane structure is thought to cause the difference in adsorption state and desorption behavior of NO.     

A DFT study of adsorption and decomposition of nitroamine molecule on Mg(001) surface

The adsorption and dissociation mechanism of NH₂NO₂ on the Mg surface have been investigated by the generalized gradient approximation of density functional theory. Calculations employ a supercell (3 × 3 × 3) slab model and three-dimensional periodic boundary conditions. The strong attractive force between oxygen and Mg atoms induces the N–O bond of the NH₂NO₂ to decompose. The dissociated oxygen atoms and radical fragment of NH₂NO₂ oxidize readily Mg atoms. The largest adsorption energy is ?860.5 kJ/mol. The largest charge transfer is 3.76 e from surface Mg atoms to fragments of NH₂NO₂. The energy barriers of N–O bond dissociation are in a range of 11.6–36.5 kJ/mol. The adsorption energy of NH₂NO₂ on the Mg surface compensates the energy needed for the N–O bond dissociation.     

Plasma Nitrogen Oxides Synthesis in a Milli-Scale Gliding Arc Reactor: Investigating the Electrical and Process Parameters

Nitrogen fixed in the form of nitrogen oxides is essential to produce fertilizers and many other chemical products, which is vital to sustain life. The performance of a milli-scale gliding arc reactor operated under atmospheric pressure has been studied for nitrogen oxides synthesis. In this work, the electrical and process parameters of the gliding arc reactor, such as frequency, pulse width, amplitude and feed ratio were investigated respectively. The experiments were performed at 1 L/min in a gliding arc discharge regime. The highest concentration of NO_x was found to be ~1 % at energy consumption of 10 kWh/kg of NO_x. Increase in frequency, pulse width and amplitude resulted in an increased specific energy input and NO_x concentration. The feed ratio (N₂/O₂) affected the amount of NO and NO₂ produced, which gives possibility to independently obtain the desired ratio of NO/NO₂ by tuning the electrical and process parameters.     

Modification of Potassium Chabazites Derived from Fly Ash by Dosing Extra Cations: Promoted CO2 Adsorption Capacities and Fine‐Tuned Frameworks

Potassium chabazite (K‐CHA), a typical microporous zeolite with excellent CO₂ separating properties, was synthesized with waste fly ash and modified via cation dosing treatments using cesium and zinc cations, respectively. The resulting CHAs were analyzed by XRF, XRD, FT‐IR, SEM, and N₂ physisorption, whose CO₂ adsorption properties were then tested on the reorganized TGA apparatus. It showed from XRF data that cesium and zinc cations were successfully imported in the original K‐CHA by cation dosing, but the CHA microstructures and morphologies of K‐CHA were perfectly retained as confirmed by XRD, FT‐IR, SEM and N₂ physisorption. Since there were still over 9 potassium cations per unit cell in cation dosed Cs‐CHA and Zn‐CHA, they both maintained the favored properties of K‐CHA as “molecular trapdoors”. In the following adsorption experiments, the CO₂ uptakes of Cs‐CHA and Zn‐CHA at 333 K and 1 bar, compared with K‐CHA, elevated from 1.70 mmol · g^–1 to 2.34 and 2.03 mmol · g^–1, and the import of zinc cation also presented a positive effect on the adsorption kinetics. Detailed comparisons suggested modifications with cesium and zinc cations fine‐tune the CHA complying with different mechanisms, and CHAs modified via cation perform more approvingly than fully ion‐exchanged ones, providing us important insights into CHA modifications and applications in practice.     

Adsorption of SO2 and chlorobenzene on activated carbon

Activated carbon is very effective for simultaneous removal of multiple pollutants. The adsorption of SO₂ and chlorobenzene modeling of VOCs on activated carbon was investigated in a fixed-bed reactor by four kinds of activated carbon. The results show that the SO₂ adsorption is affected by the BET surface and basic functional groups as C=O and π–π* groups of the carbon, while the chlorobenzene adsorption is strongly affected by the carbon pore structure, with the micropore volume deciding the adsorption amount and larger pores increasing the adsorption rate. The chlorobenzene adsorption is little affected by the chemical properties of activated carbon as the O/C ratio detected by XPS. The effect of SO₂ on the chlorobenzene adsorption was investigated, with the results showing the SO₂ seriously restricts the individual chlorobenzene adsorption and this effect becomes smaller in the presence of O₂. The adsorption products were analyzed by TPD-MS and the initial decomposition temperatures are 380 K for chlorobenzene and 500 K for SO₂, showing that SO₂ is much more stable adsorbed than chlorobenzene. The changes of the carbon functional groups that the CO₂ desorption peak emerges at 700 K and decreases at 1000 K with the chlorobenzene adsorption, were observed by TPD-MS, indicating that the lactone and quinone groups on the carbon are likely to combine with the chlorobenzene and form weakly chemisorbed chlorobenzene.     

A tunable hierarchical porous carbon from starch pretreated by calcium acetate for high performance supercapacitors

Hierarchical porous carbons (HPCs) with abundant mesopores have been prepared by a facile route from the starch that was pretreated by calcium acetate. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and N₂ adsorption–desorption tests show that hierarchical porous carbons with bimodal mesopores have been obtained. Moreover, the pore sizes are tunable by simply adjusting the reactants ratio and carbonization temperature. The as-synthesized hierarchical porous carbon materials (HPCs-2-800) possesses the highest Brunauer-Emmett-Teller (BET)-specific surface area of 464 m² g^?1 and mesoporous volume of 0.663 cm³ g^?1 at the carbonization temperature of 800 °C and starch to calcium acetate mass ratio of 2. Electrochemical measurements also display that the HPCs-2-800 electrodes have a high reversible capacity of 244 F g^?1 at the current density of 0.1 A g^?1 and 182 F g^?1 at the current density of 10 A g^?1. When the current density is elevated from 0.1 to 10 A g^?1, the high capacitance retention of 74.6 % reveals a good rate performance. Long charge–discharge cycling measurements disclose good stabilities over 25,000 cycles at different current densities of 1–10 A g^?1 (5000 cycles at each current density) for HPCs-2-800 electrode. The cycling results indicate a high capacitance retention of 99.6 % over 5000 charge–discharge cycles even at the current density of 10 A g^?1. The excellent supercapacitive performances imply that HPCs-2-800 is a promising candidate for supercapacitors.     

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H3CNO3

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface (PES) is performed for H₃CNO₃ using the Scaled Hypersphere Search‐Anharmonic Downward Distortion Following (SHS‐ADDF) method. The molecular formula of H₃CNO₃ includes functional groups of CH₃, OH, NH₂, COOH, NO, NO₂, and NO₃, which are very important in connection with amino acids and NOx. Geometrical structures and interconversion pathways are disclosed after 18719781 force calculations and 534726 Hessian calculations at the level of B3LYP/6‐31G(d). The explored results are confirmed to be valid, especially for the important lower energy regions, by re‐optimization at the higher level of B3LYP/6‐311++G(d,p). A global reaction route‐mapping using SHS‐ADDF demonstrates the entire view and undeveloped landscapes on PES of H₃CNO₃. Typical compounds of H₃CNO₃, aminoxy formic acid, hydroxycarbamic acid, aminoperformic acid, hydroxymethyl nitrite, nitromethanol, methyl nitrate, methyl peroxynitrite, and dioxaziridine, are well separated from others by very high energy‐barriers. The stable‐most conformer of H₃CNO₃ is difficult to be determined, because of seven structures existing with nearly the same energies within 5.7 kJ/mol at the level of CCSD(T)/aug‐cc‐pVTZ. © 2017 Wiley Periodicals, Inc.     

NO2在Ag/Pt(110)双金属表面上的吸附和分解

利用俄歇电子能谱(AES)和程序升温脱附谱(TDS)研究了NO₂在Ag/Pt(110)双金属表面的吸附和分解.室温下NO₂ 在Ag/Pt(110)双金属表面发生解离吸附, 生成NO(ads)和O(ads)表面吸附物种. 在升温过程中NO(ads)物种发生脱附或者进一步分解. 500 K时NO₂在Ag/Pt(110)双金属表面发生解离吸附生成O(ads)表面吸附物种. Pt 向Ag传递电子, 从而削弱Pt－O键的强度, 降低O(ads)从Pt 表面的并合脱附温度. 发现能够形成具有稳定组成的Ag/Pt(110)合金结构, 其表现出与Pt(110)-(1×2)相似的解离吸附NO₂能力, 但与O(ads)的结合明显弱于Pt(110)-(1×2). 该AgPt(110)合金结构是可能的低温催化直接分解氮氧化物活性结构.     

高硅 Na-ZSM-5 分子筛表面 NO 的常温吸附-氧化机理

 采用程序升温表面反应 (TPSR) 和原位漫反射红外光谱 (DRIFTS) 等手段研究了常温下 NO 和 O₂ 在高硅 Na-ZSM-5 分子筛上吸附-氧化反应机理. 结果表明, Na-ZSM-5 分子筛上 NO 的催化氧化过程中伴随着显著的 NO₂ 物理吸附, 表现为 NO 氧化和 NO₂ 吸附间的动态平衡. Na-ZSM-5 分子筛表面 NO_x 吸附物种的 TPSR 和原位 DRIFTS 表征表明, 化学吸附的 NO 和气相中的 O₂  在 Na-ZSM-5 表面反应生成吸附态的 NO₃, 并继续与 NO 作用生成弱吸附的 NO₂  和 N₂ O₄, 它们吸附饱和后释放出来; 其中, 强吸附的 NO₃ 在 NO 氧化过程中起到了反应中间体的作用, 同时也促进了 NO 的吸附.     

Amino-functionalized pore-expanded SBA-15 for CO2 adsorption

The adsorption of CO₂ on pore-expanded SBA-15 mesostructured silica functionalized with amino groups was studied. The synthesis of conventional SBA-15 was modified to obtain pore-expanded materials, with pore diameters from 11 to 15 nm. Post-synthesis functionalization treatments were carried out by grafting with diethylenetriamine (DT) and by impregnation with tetraethylenepentamine (TEPA) and polyethyleneimine (PEI). The adsorbents were characterized by X-ray diffraction, N₂ adsorption–desorption at 77 K, elemental analysis and Transmission Electron Microscopy. CO₂ capture was studied by using a volumetric adsorption technique at 45 °C. Consecutive adsorption–desorption experiments were also conducted to check the cyclic behaviour of adsorbents in CO₂ capture. An improvement in CO₂ adsorption capacity and efficiency of amino groups was found for pore-expanded SBA-15 impregnated materials in comparison with their counterparts prepared from conventional SBA-15 with smaller pore size. PEI and TEPA-based adsorbents reached significant CO₂ uptakes at 45 °C and 1 bar (138 and 164 mg CO₂/g, respectively), with high amine efficiencies (0.33 and 0.37 mol CO₂/mol N), due to the positive effect of the larger pore diameter in the diffusion and accessibility of organic groups. Pore-expanded SBA-15 samples grafted with DT and impregnated with PEI showed a good stability after several adsorption–desorption cycles of pure CO₂. PEI-impregnated adsorbent was tested in a fixed bed reactor with a diluted gas mixture containing 15 % CO₂, 5 % O₂, 80 % Ar and water (45 °C, 1 bar). A noteworthy adsorption capacity of 171 mg CO₂/g was obtained in these conditions, which simulate flue gas after the desulphurization step in a thermal power plant.     

Adsorption Behavior of Nitrogen Monoxide on KxGaxSn8−xO16 Hollandite

Fine powder of K _x Ga _x Sn_8–x O₁₆ hollandite was prepared by the sol-gel process using metal alkoxides, and the adsorption behavior of nitrogen monoxide (NO) on it was examined by temperature programmed desorption (TPD) method and in situ diffuse reflectance fourier transform infrared spectroscopy. Any species other than nitrogen monoxide were not detected in the TPD measurement, and the profile showed three stages between 420 and 880 K which were regarded as the desorption of chemically adsorbed NO _x species. This desorption behavior seems well consistent with the spectral changes in the FT-IR measurement. The absorption band at 1270 cm^–1 was decayed in the first stage from 420 to 640 K, and the bands at 1235 and 1570 cm^–1 in the second stage from 640 and 770 K. In the third stage above 770 K, the strong band at 1340 cm^–1 disappeared. These NO _x species on the hollandite were estimated to have a form of NO₃ ^– in the first and second stages and a form of NO₂ ^– in the third stage, considering the data on adsorption of nitrogen oxides on La₂O₃ and CaO.