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The methanol decomposition reaction has gained substantial attention due to the wide range of applications that its intermediates offer. In this work, methanol (CH3OH) decomposition on Copper-embedded graphene (CuG) surface has been investigated via density functional theory with Grimme-D2 dispersion correction. The charge density of the CuG surface has been analyzed and the redistribution of the electron density of the surface has been represented via the electron density difference (EDD) map. Moreover, the decomposition reaction mechanism of CH3OH on the CuG surface through the cleavage of C–H, O–H and C–O bonds has been investigated in detail. In the initial state, the C–O and O–H bonds of CH3OH have similar activation barriers, thereby the adsorption and degradation mechanism of the intermediate states arising through O–H bond cleavage on the CuG surface has been investigated. In addition, the charge density calculations of the transition state geometries have been conducted and examined with EDD maps. The results have revealed that the previously adsorbed oxygen molecule exhibited high catalytic activity towards O–H decomposition compared to the bare surface. The CuG surface has offered higher activity on the C–H bonds compared to the C–O bonds of the intermediate states generated by CH3OH decomposition. The results revealed that the proposed CuG structure can be utilized as an alternative electrode catalyst that can prevent the CO poisoning issue in direct methanol fuel cells. © 2021 Hydrogen Energy Publications LLC

The plane exposure of support vitally affects the catalytic performance of the catalyst. In this work, CeO2 nanorods ((1 1 0) plane exposure), nano-octahedrons ((1 1 1) plane exposure) and nano-cubes ((1 0 0) plane exposure) were prepared as the supports of Pt/CeO2 samples to investigate the effect of CeO2 plane exposure on total toluene oxidation. Characterizations reveal that the (1 1 0) plane of CeO2 is more helpful to the dispersion of Pt species, followed by (1 1 1) face. The improved dispersion of Pt species can enhance the metal-supports interaction, which promotes the electron transfer of CeO2 carrier to Pt nanoparticles and the adsorption-activation of O2, thereby facilitating the total oxidation of toluene via the Langmuir–Hinshelwood (L-H) mechanism. Therefore, Pt/CeO2-r (nanorods) sample expresses the most excellent catalytic performance of toluene oxidation. Finally, the procedure of toluene total oxidation was studied by in-situ DRIFT. We expect that this work can contribute to the development of an effective sample for the decomposition of volatile organic compounds (VOCs).

No consensus has been reached on the role of reducible and irreducible supports on the reaction pathway of CO oxidation over supported metal catalysts. Here, colloidal ligand-free Pt nanoparticles were deposited on Al2O3 and CeO2 to investigate the support effect in CO oxidation by in situ diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS) and mass spectrometry (MS). On Pt/Al2O3, the carbonate-like intermediates accumulate and do not decompose to CO2 at the ignition temperature (150 °C) or above; the conversion of CO to CO2 follows classic Langmuir−Hinshelwood (L–H) mechanism with direct reaction of CO and O2 on Pt. Whereas for Pt/CeO2, the CO conversion to bidentate carbonate (b-CO32−) species followed by decomposition to CO2 is a main reaction pathway leading to its high reactivity at low temperature (75 °C). CeO2 facilitates the activation of oxygen to produce the carbonate-like intermediates and further decomposition to CO2, which resulted in a lower ignition temperature.

The cognition of active sites in the Ni-based catalysts plays a vital role and remains a huge challenge in improving catalytic performance of low temperature CO2 dry reforming of methane (LTDRM). In this work, typical catalysts of SiO2 and γ-Al2O3 supported Ni and Ni-Ce were designed and prepared. Importantly, the difference in the chemical speciations of active sites on the Ni-based catalysts is revealed by advanced characterizations and further estimates respective catalytic performance for LTDRM. Results show that larger [ Ni n 0 ] particles mixed with [Ni-O-Sin]) species on the Ni/SiO2(R) make CH4 excessive decomposition, leading to poor activity and stability. Once the Ce species is doped, however, superior activity (59.0% CH4 and 59.8% CO2 conversions), stability and high H2/CO ratio (0.96) at 600 °C can be achieved on the Ni-Ce/SiO2(R), in comparison with other catalysts and even reported studies. The improved performance can be ascribed to the formation of integral ( [ Ni n 0 ] -[CeIII-□-CeIII]) species on the Ni-Ce/SiO2(R) catalyst, containing highly dispersed [ Ni n 0 ] particles and rich oxygen vacancies, which can synergistically establish a new stable balance between gasification of carbon species and CO2 dissociation. With respect to Ni-Ce/γ-Al2O3(R), the Ni and Ce precursors are easily captured by extra-framework Aln-OH groups and further form stable isolated ( [ Ni n 0 ] -[Ni-O-Aln]) and [CeIII-O-Aln] species. In such a case, both of them preferentially accelerate CO2 adsorption and dissociation, causing more carbon deposition due to the disproportionation of superfluous CO product. This deep distinguishment of chemical speciations of active sites can guide us to further develop new efficient Ni-based catalysts for LTDRM in the future.

The fast decomposition of peroxides (M2O2, where M = H+, Li+) at room temperature has gained increased attention given its relevance, from propulsive systems to metal-O2 conversion batteries. This study describes, by a rational design of experiment, the influence of selected parameters such as: pH, initial concentration of K2CO3, precipitate aging, precipitate washing, and thermal treatment for the hydrotalcite co-precipitation, characterizing it for each synthesis variable. The results show that hydrotalcites can efficiently be converted in Co-Mn-Al spinels and as a result, a new highly active Co2Mn0.5Al0.5O4 spinel oxide was synthesized after thermal treatment. Its activity and mechanical resistance were tested in a micro-thruster reactor where it showed total decomposition (> 98%) of H2O2 and in a Li-O2 battery, with increased cyclability, been able to reduce the charging potential in ~200 mV. These encouraging results enhance the importance not only of this class of material, but also, the importance of robust synthesis methodologies for reproducible results.

In this study, several noble zeolites (SA-600A)-based catalysts supported with RuCl3.nH2O and LiOH·H2O materials were investigated for H2 production from NH3 decomposition. The synthetic catalysts were simultaneously prepared at different supported materials mixing ratios. The effect of initial mixing of Li and Ru on catalyst performance compared to simultaneous mixing was studied. All catalysts were tested for hydrogen production from NH3 decomposition at atmospheric pressure, temperature range of 200–670 oC, and gas hourly space velocity (GHSV) of 3000 h−1. It was found that the simultaneous and initial mixing of Li and Ru has the same NH3 decomposition results. The zeolite-based catalyst was enhanced with the Ru supported material mixing ratio increase. Among all the synthetic catalysts the catalyst type of 40 g (SA-600A)/5 g RuCl3.nH2O/3 g LiOH·H2O) showed the highest catalyst activity. The catalyst with a mixing ratio of 40 g (SA-600A)/5 g RuCl3.nH2O/3 g LiOH·H2O) was registered the peak NH3 conversion 99.87% at lower temperature of 490 °C.

The phosphorus-doped carbon materials as one of novel carbon catalysts towards the hydrogen evolution reaction (HER) have attracted considerable attention over the past years. However, the role of C-P species palyed in the HER activity is still not clear up to now. Phosphorus-doped carbon nanotubes (P-CNTs) were prepared by chemical vapor deposition and annealed at 900, 1000 and 1200 ℃ to remove all or parts of phosporus species, resulting in four samples with different proportions of graphite-, pyridine- and pyrrole-like P species. The correlations between their HER activity and the contents of three types of P species were investigated. Results showed that the content of graphite-like P decreased with the annealing temperature and no graphite-like P was retained at 1200℃. The HER activity increased with the annealing temperature and the one annealed at 1200 ℃ had the highest HER activity in an acid medium with an overpotential of 0.266 V at a current density of 10 mA/cm−2. Density functional theory calculations revealed that the pentagon- and nine-membered ring defects formed by the destruction of graphite-P species contributed mainly to the HER activity, which gave a deep insight into the active sites for HER.

In this work, six energetic complexes were prepared and used as promoters for the hypergolic reaction of 1-ethyl-3-methylimidazolium cyanoborohydride [EMIM][BH3CN] and 90% H2O2. The structures of these compounds were studied by FT-IR spectroscopy, powder XRD, and single crystal X-ray diffraction. The results revealed that all the compounds were iso-structural and each metal centre was coordinated with four organic ligands and two counter ions. The decomposition temperatures of these compounds ranged from 169.6-255.9 °C. After adding 10 wt.% of prepared complexes to an ionic liquid, [EMIM][BH3CN], the shortest ignition delay time achieved was 94 ms. Moreover, the formed homogenous catalytic fuels had similar densities, thermal stabilities, as well as specific impulses similar to that of pure [EMIM][BH3CN]. The simple preparation method, excellent yield, as well as high performance of these compounds make them promising promoters for use in green hypergolic bipropellants.

Exploring an alternative strategy with high efficiency and low cost to abate formaldehyde (HCHO) in indoor environment, is of increasing significance for people’s health. CeO2 catalysts prepared by hydrothermal, precipitation and calcination methods were investigated for HCHO removal at ambient temperature. It is found that indoor fluorescent light visibly boosts the catalytic performance of CeO2 catalysts for HCHO decomposition at ambient temperature. Among the CeO2 catalysts, CeO2 prepared from hydrothermal method (CeO2-H) exhibits a superior catalytic performance and an excellent durability by eight recycle times. Based on the characterization and analysis, the excellent catalytic performance of CeO2-H is mainly contributed by its abundance of surface oxygen vacancies, and photogenerated electrons and hole activated by fluorescent light. This work shows a potential practicability in HCHO pollution elimination by taking full advantage of the existing lighting in indoor environments.

An effective strategy involving a suitable carrier is needed to improve the dispersion, combustion and catalytic performances of catalyst nanoparticles. Herein, a Bi2WO6/g-C3N4 composite employing g-C3N4 as the catalyst carrier was prepared by a one-step in situ hydrothermal method, which was used as the combustion catalyst of solid propellants. The catalyst’s structure, morphology and its catalytic decomposition of several energetic materials were characterized by a series of analyses. The optimal ratio of g-C3N4 and Bi2WO6 was systematically determined. The results demonstrate that Bi2WO6/g-C3N4 (4:6) composite can diminish the decomposition temperatures of ammonium perchlorate (AP), cyclotrimethylenetrinitramine (RDX), dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) and cyclotrimethylenetrinitramine+nitrocellulose (RDX+NC) by 25.0, 5.2, 24.0 and 1.2 (4.9) °C, and reduce their apparent activation energy by 59.5, 116.7, 11.6 kJ·mol-1, respectively. Moreover, the laser ignition tests indicate that Bi2WO6/g-C3N4 can effectively promote the ignition performance of RDX and RDX+NC. A possible mechanism of Bi2WO6/g-C3N4 on AP was proposed. The g-C3N4 catalyst carrier is superior to GO carrier due to its low cost, simple synthesis process, improved combustion and catalytic performances, as well as abundant N content. These make it have broad engineering application prospects in solid propulsion and several other energetic materials.

In recent years, MoS2 catalyzed/cocatalyzed Fenton/Fenton-like systems have attracted wide attention in the field of pollution control, but there are few studies on the effect of H2O2 feeding way on the whole Fenton process. Here, we report a new type of composite catalyst (MoS2-Fex) prepared in a simple way with highly dispersed iron to provide more active sites. MoS2-Fex was proved to possess selectivity for singlet oxygen (1O2) in effectively degrading sulfadiazine with a wide pH adaptability (4.0∼10.0). Importantly, the mechanism of the interaction between H2O2 and MoS2 on the Fenton reaction activity was revealed through the combination of experiment and density functional theory (DFT) calculations. Compared to the traditional “a large amount for one time” feeding way of H2O2, the “small amount for multiple times” of H2O2 feeding way can increase the degradation rate of sulfadiazine from 36.9% to 91.1% in the MoS2-Fex heterogeneous Fenton system. It is demonstrated that the “small amount for multiple times” of H2O2 feeding way can reduce the side reaction of decomposition of H2O2 by MoS2 and effectively improve the utilization rate of H2O2 and the stability of MoS2-Fex. Compared with Fe2O3-based Fenton system, MoS2-Fex can significantly save the amount of H2O2. Compared with nano-iron powder, the formation of iron sludge in MoS2-Fex system was significantly reduced. Furthermore, long-term degradation test showed that the MoS2-Fe75/H2O2 system could maintain the effectiveness of degrading organic pollutants for 10 days (or even longer). This study has a guiding significance for the large-scale treatment of industrial wastewater by improved Fenton technology in the future.

Formic acid is one of the key components in green chemistry being involved in energy storage, production of chemical intermediates and fuel components. Therefore the knowledge of its stability is of crucial importance and a systematic study of its decomposition is needed. The kinetics of formic acid decomposition to hydrogen and carbon dioxide was investigated in a laboratory-scale fixed bed reactor at 150–225 °C and atmospheric pressure. Palladium nanoparticles deposited on porous active carbon Sibunit were used as the heterogeneous catalyst. The catalyst was characterized by nitrogen physisorption and high-resolution transmission electron microscopy. The average palladium nanoparticle size was 5–6 nm. The impacts of mass transfer resistance and formic acid dimerization were negligible under the reaction conditions. Prolonged experiments revealed that the catalyst had a good stability. Hydrogen and carbon dioxide were the absolutely dominant reaction products, whereas the amounts of carbon monoxide and water were negligible. The experimental data were described with three kinetic models: first order kinetics, two-step adsorption-reaction model and multistep adsorption-decomposition model of formic acid. The multistep model gave the best description of the data.

Burning lignocellulosic biomass wastes in an outdoor atmosphere has placed heavy burden on ecological environment and increased risk on human health. Converting solid agricultural wastes into functional materials is a research hotspot. In this study, N-doped and CoO-loaded carbocatalyst (CoO-N/BC) was successfully synthesized from the cotton stalk biomass via a simple synthesis process of impregnation and carbonization. Compared with cotton stalk biomass derived pristine biochar, the CoO-N/BC possessed a higher specific surface area (466.631 m2 g-1 vs 286.684 m2 g-1) as well as a better catalytic performance in the activation of peroxymonosulfate (PMS) for CIP degradation. The superior catalytic efficiency was ascribed to the directional flow of electrons on the well-organized carbon network of CoO-N/BC, which accelerated electron migration and improved electron conduction ability. Based on the results of radical quenching experiment and electron paramagnetic resonance (EPR), both radical and non-radical process conjointly led to the stepwise decomposition of CIP, and singlet oxygen (1O2) mediated non-radical pathway was discovered to play a dominant role. Besides, the carbon-bridge mediated non-radical pathway was proved to accelerate this degradation process through the experiments of prolong the time of adding CIP at different time intervals. Nitrogen doped sites and CoO active sites as well as defects formed in sp2-hybridized carbon network were supposed to be the active sites for PMS. Furthermore, EIS and LSV were employed to confirm the electron transfer mediated non-radical process of reaction system. This work provides a modified strategy for the disposition of lignocellulosic biomass wastes and illuminates the underlying mechanism of heterogeneous catalysis by CoO-N/BC.

CO2 hydrogenation to methanol was investigated over CuZnIn/MZrOx (M = La, Y or Ti) catalysts at 20 bar and at 225 °C with the purpose to elucidate the effects of the metal oxide promoter for ZrO2 and InOx for CuZnOx on reaction scheme of product formation, catalyst activity and product selectivity. Although the additives do not affect the overall scheme of product formation, they are relevant for the rates of direct CO2 conversion into methanol or CO and of methanol decomposition to CO and H2. This is due to their influence on dispersion of CuOx and the strength of basic sites for CO2 adsorption. Highly dispersed CuOx species are essential for CO2 conversion but not for methanol selectivity. The selectivity is improved over polymerized CuOx with strong basicity. This catalyst property can be controlled through promoting of (i) ZrO2 with La2O3/Y2O3 or (ii) CuZnOx with InOx. The latter promoter is crucial for hindering the undesired methanol decomposition to carbon monoxide.

In this study, a graphitic carbon nitride (g-C3N4) based ternary catalyst CuO/CuFe2O4/g-C3N4 (CCCN) is successfully prepared thorough calcination method. After confirming the structure and composition of CCCN, the as-synthesized composites are utilized to activate persulfate (PS) for the degradation of organic contaminant. While using tetracycline hydrochloride (TC) as pollutant surrogate, the effects of initial pH, PS and catalyst concentration on the degradation rate are systematically studied. Under the optimized reaction condition, CCCN/PS is able to give 99% degradation extent and 74% chemical oxygen demand removal in assistance of simulated solar light, both of which are apparently greater than that of either CuO/CuFe2O4 and pristine g-C3N4. The great improvement in degradation can be assignable to the effective separation of photoinduced carriers thanks to the integration between CuO/CuFe2O4 and g-C3N4, as well as the increased reaction sites given by the g-C3N4 substrate. Moreover, the scavenging trials imply that the major oxidative matters involved in the decomposition are hydroxyl radicals (•OH), superoxide radicals (•O2−) and photo-induced holes (h+).

Direct synthesis of graphene on insulating substrates is highly desirable for practical applications. Herein, we present a new fabrication method for graphene on quartz which enables the direct growth of high-quality and large-scale graphene films with no metal involved. The growth rate of graphene on insulating substrates was typically extremely slow due to the low catalytic activity and the slow diffusion speed of carbon species on them. Thus, an extra catalyst is required. Instead of metal elements, such as Cu, Ni, and Ga, highly-defective graphene films were applied as the catalyst for methane decomposition. The key feature of our approach is that carbon itself was used as the catalyst for graphene fabrication, which completely avoided the contamination of other elements. As a result, the growth rate of graphene films increased significantly compared to the conventional CVD method. The excellent quality of graphene glass was verified by a series of experimental characterization and the fabrication of a transparent heating device without any transfer process. In addition, the energy barrier of the decomposition of methane was explored using the first principles calculation, which further confirmed the catalytic behavior of highly-defective graphene films.

Alumina supported Pd catalyst (Pd/Al2O3) is active for complete oxidation of methane, while often suffers transient deactivation during the cold down process. Herein, heating and cooling cycle tests between 200 and 900°C and isothermal experiments at 650°C were conducted to investigate the influence of NOx on transient deactivation of Pd/θ-Al2O3 catalyst during the methane oxidation. It was found that the co-fed of NO alleviated transient deactivation in the cooling ramp from 800 to 500°C, which was resulted from the in situ formation of NO2 during the process of methane oxidation. Over the Pd/θ-Al2O3, thermogravimetric analysis and O2 temperature programmed oxidation measurements confirmed that transient deactivation was due to the decomposition of PdO particles and the hysteresis of Pd reoxidation, while the metal Pd entities were less active for methane oxidation than the PdO ones. CO pulse chemisorption and scanning transmission electron microscopy characterizations rule out the NO2 effect on Pd size change. Powder X-ray diffraction and X-ray photoelectron spectroscopy characterizations were used to obtain palladium status of Pd/θ-Al2O3 before and after reactions, indicating that in lean conditions at 650°C, the presence of NO2 increases the content of active PdO on the catalyst surface, thus benefits methane oxidation. Homogeneous reaction between CH4, O2, and NOx may be partially responsible for the alleviation above 650°C. The interesting research of alleviation in transient deactivation by NOx, the components co-existing in exhausts, are of great significance for the application.

A highly efficient and stable hydrotalcite-derived Cu-MgAlO catalyst was developed for the partial oxidation of cyclohexane with molecular oxygen. The physical-chemical properties of Cu-MgAlO catalysts were studied, and the results indicated that the copper component had been successfully introduced into the hydrotalcite unit layer structure. The catalytic reaction results showed that copper as the active species could activate C-H bond and effectively promote the decomposition of cyclohexyl hydroperoxide (CHHP) to KA oil. 8.3% of cyclohexane conversion and 82.9% of selectivity for KA oil were obtained over 9%Cu-MgAlO catalyst at 150 °C with 0.6 MPa of oxygen pressure for 2 h. Especially, its catalytic performance was still stable after five runs.

A once overlooked source of electrolyte degradation incurred by dissolved manganese (II) species in lithium-ion batteries has been identified recently. In order to deactivate the catalytic activity of such manganese (II) ion, 1-aza-12-crown-4-ether (A12C4) with cavity size well matched manganese (II) ion is used in this work as electrolyte additive. Theoretical and experimental results show that stable complex forms between A12C4 and manganese (II) ions in the electrolyte, which does not affect the solvation of Li ions. The strong binding effect of A12C4 additive reduces the charge density of manganese (II) ion and inhibits its destruction of the PF6− structure in the electrolyte, leading to greatly improved thermal stability of manganese (II) ions-containing electrolyte. In addition to bulk electrolyte, A12C4 additive also shows capability in preventing Mn2+ from degrading SEI on graphite surface. Such bulk and interphasial stability introduced by A12C4 leads to significantly improved cycling performance of LIBs.

The influence of Ni-hydrotalcite (HT) loading on the activity and stability of Ni-HT supported on activated carbon (Ni-HT/AC) was investigated for fermentative hydrogen production. The basic sites of Ni-HT loading on AC support significantly boosted the catalytic performance with the initial faster rate. The combined function catalyst of Ni-HT/AC facilitates the rapid decomposition of saccharides and high selectivity to fructose that attained the maximum hydrogen production within 24 h. The optimum dose of Ni-HT/AC at 8.33 g/L showed a 25.84% increment over the control. In addition, shortening the lagging phase time at 1.50 h was achieved. The high adsorption capacity of lactic acid was induced with the basic sites of Ni-HT/AC. However, a deactivation of the Ni-HT/AC during prolonged fermentation was associated with metabolites formation, causing the leaching of Mg2+ ions from the surface of AC supported Ni-HT and reducing surface basicity of Ni-HT/AC.

Developing low-temperature SO2-tolerant catalysts for the selective catalytic reduction of NOx is still a challenging task. The sulfation of active metal oxides and deposition of ammonium bisulfate deactivate catalysts, due to the difficult decomposition of the as-formed sulfate species at low temperatures ( 300°C); however, the SO2-tolerant mechanism of metal sulfate catalysts is still ambiguous. In this study, Fe2(SO4)3/TiO2 and Ce2(SO4)3/TiO2 catalysts were prepared using the corresponding metal sulfate salt as the precursor. These catalysts were tested for their low-temperature activity and SO2 tolerance activity. Compared to Ce2(SO4)3/TiO2, Fe2(SO4)3/TiO2 showed significantly better low-temperature activity and SO2 tolerance. It was demonstrated that less surface sulfate species formed on Fe2(SO4)3/TiO2 and Ce2(SO4)3/TiO2. However, the presence of NO and O2 could assist the decomposition of NH4HSO4 over Fe2(SO4)3/TiO2 at a lower temperature, endowing Fe2(SO4)3/TiO2 with better low-temperature SO2 tolerance than Ce2(SO4)3/TiO2. This study unraveled the SO2-tolerant mechanism of Fe2(SO4)3/TiO2 at lower temperatures (

DBD-catalytic system has been widely studied for volatile organic compounds abatement, whereas how to obtain high mineralization rate and low zone emission synchronously remains a challenge. In view of this, a new type of multi-stage DBD-catalytic system (MS1) was established to abatement toluene in this study. The mineralization rates of reactors IPC (63.81%) and MS1 (61.14%) were much higher than MS2, PPC1 and PPC2 reactors, which were 48.36%, 46.84%, and 5.8% at 33.8 (Vp-p) kV, respectively. For export ozone concentration, IPC reactor had the highest concentration of 160 ppm, and the values of reactors MS1, MS2, PPC1, and PPC2 were 79, 34.2, 34.25 and 29 ppm, respectively. The catalyst filled in zone II can be utilized to further decompose the residual toluene and intermediates and also promote the decomposition of ozone, which lead to the superior performance of the MS1 reactor. The influence of applied voltage, adsorbed amount, and discharge time on the toluene removal performance was investigated to optimize the operation parameters of MS1 reactor, their appropriate values were 28.3–31.1 (Vp-p) kV, 0.179–0.223 mmol, ∼1 h, respectively. Lastly, the contribution of disparate zones in multi-stage DBD-catalytic system to the toluene degradation were elucidated on the basis of the GC–MS results.

The effect of regeneration conditions on the cyclic sorption-enhanced steam reforming of ethanol (SESRE) in a fixed-bed reactor was investigated. Columnar Ni–Ca catalysts were used in the cyclic SESRE experiments. The effects of different parameters, including temperature, purge direction, and purge gas on the regeneration process were discussed. The experimental results reveal that the regeneration temperature strongly affected not only the CO2 desorption rate but also the durability of the CaO sorbent. The stability of the CaO sorbent within the Ni–Ca catalyst was improved owing to the formation of Ca12Al14O33. Moreover, the type of purge gas (N2 or air) for regeneration had negligible effect on the CO2 capture performance of the Ni–Ca catalyst. For regeneration by air purging, coke decomposition over the Ni–Ca catalyst was accompanied by a slight decline in the activity of the Ni catalyst, which was attributed to the cyclic Ni redox.

Porous carbon fibers catalysts have been prepared by electrospinning of Alcell lignin, a green carbon precursor, which could be obtained as by-product in wood-to-ethanol biorefineries. The addition of H3PO4, a well-known chemical activation agent, to the electrospinning lignin solutions, at different mass ratios and the use of different carbonization temperatures, between 500 and 1600 °C, were analyzed in order to obtain carbon fibers with a large variety of porosity and chemical surface properties. Isopropanol decomposition was used as a catalytic test. Phosphorus-containing carbon fibers showed acid character and high catalytic activity, achieving propylene selectivity of 100 % under inert atmosphere. However, the use of air atmosphere increases the isopropanol conversion but produces the formation of acetone, via oxidative dehydrogenation, at low temperatures (∼20 %). Ethanol and methanol decomposition were also evaluated in air stream for the most active phosphorus-containing carbon catalyst, showing improved alcohol conversions with minimal gasification of the carbon fibers. These results confirmed that phosphorus-containing carbon fibers prepared by electrospinning of lignin solutions were excellent catalysts for alcohol dehydration reactions.

Ferroelectric BaTiO3/ZnO heterojunction catalysts synthesised via the sol–gel method present obvious enhancements in spontaneous polarisation-driven Fenton-like catalytic activity. In this study, the oxidative decomposition of methylene blue (MB) dye was used as a model reaction. Pure BaTiO3-activated potassium monopersulphate (PMS) could decompose up to 48% of MB dye in an aqueous solution after 40 min. MB degradation rate firstly increased and then decreased as the ZnO content of the ferroelectric BaTiO3/ZnO heterojunction materials was increased. The maximum degradation rate of 100% and good cycling stability were observed when the BaTiO3:ZnO molar ratio was 1:1. Three active species, namely, holes (h+), sulphate radicals (SO4•−) and hydroxyl radicals (OH•), were produced following the spontaneous polarisation-driven catalytic degradation of the dye. Amongst these species, h+ and SO4•− were the main active species. Enhancements in the Fenton-like catalytic activity of BaTiO3/ZnO may be attributed to the formation of semiconductor heterojunctions, which could improve the spontaneous polarisation strength of ferroelectric BaTiO3, promote the effective separation of e−–h+ pairs and accelerate PMS activation. In summary, a novel PMS activation method was developed to provide a nontoxic, efficient and environmentally friendly technology for the degradation of organic pollutants.

The design and fabrication of efficient catalysts for ammonium perchlorate (AP) decomposition is crucial for the performance of composite solid propellants. Herein, a novel hierarchical structure material of Cu-WO3 nanowire arrays on a nanoflower flake (Cu-WO3 NANF) was synthesized by a facile hydrothermal reaction. The negatively charged (001) polar facets of hexagonal WO3 and the action of Cu2+ induced growth were two important factors for the formation of hierarchical structures. The Cu-WO3 NANF exhibited remarkable catalytic activity for the thermal decomposition of AP. The temperature and activation energy of high temperature AP decomposition were significantly decreased to 378.3 °C and 147.01 kJ mol−1, respectively, which are attributed to the more oxygen vacancies and lower band gap energy of the Cu-WO3 NANF. Thus, it was excited at a lower heat to produce activated species. Under the strong adsorption of Cu-WO3 NANF surface Lewis acid, the activated species can react with NH3 quickly and deeply to produce N2, N2O, NO2 and NO gases, accompanied by a heat release of up to 1118 J g−1. The proposed catalytic mechanism was further corroborated by the in situ TG-MS result. This facile strategy provided a new idea for the design of hierarchical catalysts, and our research opened up a new field for WO3 applications.

On-site produced hydrogen from ammonia decomposition can directly fuel solid oxide fuel cells (SOFCs) for power generation. The key issue in ammonia decomposition is to improve the activity and stability of the reaction at low temperatures. In this study, proton-conducting oxides, Ba(Zr,Y) O3-δ (BZY), were investigated as potential support materials to load Ni metal by a one-step impregnation method. The influence of Ni loading, Ba loading, and synthesis temperature, of Ni/BZY catalysts on the catalytic activity for ammonia decomposition were investigated. The Ni/BZY catalyst with Ba loading of 20 wt%, Ni loading of 30 wt%, and synthesized at 900 °C attained the highest ammonia conversion of 100% at 600 °C. The kinetics analysis revealed that for Ni/BZY catalyst, the hydrogen poisoning effect for ammonia decomposition was significantly suppressed. The reaction order of hydrogen for the optimized Ni/BZY catalyst was estimated as low as −0.07, which is the lowest to the best of our knowledge, resulting in the improvement in the activity. H2 temperature programmed reduction and desorption analysis results suggested that a strong interaction between Ni and BZY support as well as the hydrogen storage capability of the proton-conducting support might be responsible for the promotion of ammonia decomposition on Ni/BZY. Based on the experimental data, a mechanism of hydrogen spillover from Ni to BZY support is proposed.

An effective decontamination method for soils remediation is a long-standing challenge. Herein, hydrogen peroxide (H2O2) was spontaneously produced in thin films generated by evaporating almost all the water. H2O2-sensitive test strips and oxidation of 2-hydroxybenzophenone to 2-hydroxyphenyl benzoate confirmed the generation of H2O2. Experiments in which reaction time and temperature were varied and established dependence of H2O2 production on the long-lasting thin films. H2O2 production was independence of irradiation and oxygen from air or dissolved oxygen. Spin-trapping probe experiments suggested that electric fields at the thin interfacial films enabled OH- to hydroxyl radicals and further recombination to H2O2. As a proof-of-principle experiment, perfluorooctanoic acid (PFOA) was effectively degraded on the thin films without catalysts and UV irradiation could further facilitate the degradation. A degradation mechanism was proposed involving the PFOA radicals on thin interfacial films and the subsequent decomposition of the radicals with successive loss of CF2. These findings have important implications for the development of decontamination method for soils remediation based on thin films, because thin film formats are ubiquitous at the surface of soils and when aerosols falling onto a substrate.

Facilitating polysulfide conversion by electrocatalysis is a promising strategy to suppress shuttle effect in lithium-sulfur (Li-S) batteries, yet the active sites in electrocatalysts are gradually passivated by continuous formation of Li2S passivation layer over cycling, making it challenging to achieve steady conversion of sulfur species. Herein, a strategy of reactive Li2S collaborated with dual-directional Fe3C electrocatalyst is proposed to achieve fast and continuous conversion of sulfur species for drastically boosting the performance of Li-S batteries. During the reduction process, reactive Li2S with unique three-dimensional porous structure is precipitated on Fe3C surface, which not only shortens ion/electron diffusion path but also exposes and retains more active sites in Fe3C. While for the following oxidation process, Fe3C also promotes the decomposition of reactive Li2S to refresh electrocatalyst surface. Therefore, the high catalytic activity of Fe3C is well retained during the entire electrochemical process, as verified by comprehensive experimental and theoretical calculation results. Eventually, Fe3C enables stable operation of high-areal-capacity Li-S batteries (> 6.0 mAh cm−2) under a wide-temperature range (-10 to 40 °C). Our strategy of coupling reactive Li2S with a bidirectional electrocatalyst provides a new avenue for developing high-energy and wide-temperature Li-S batteries.

Conversion of waste lipid biomass into renewable fuels using sub- and supercritical water provides an alternative green approach in contrast with the current treatment methods. However, the reaction network of unsaturated lipids in sub- and supercritical water has not been clarified. Unsaturated lipids are found abundantly in waste lipid biomass, making the establishment of their reaction network essential. In this study, the reaction of crotonic acid (CA) as a model unsaturated lipid in sub- and supercritical water was clarified through an in-depth study of its reaction pathways and kinetics. The experiments were conducted at temperatures from 300 to 415 °C, a pressure of 25 MPa, and residence times from 30 to 150 s in a continuous flow process. The main products in the initial stage of the reaction were butyric acid (BA) and propene. Based on the temperature dependence experiments, the CA conversion increased along with temperature and residence time. Based on the product distribution, two main decomposition pathways were identified in the initial stage of the CA reaction. The first is CA direct decarboxylation and the second is CA hydrogenation followed by BA decarbonylation. Examination of the kinetic rates revealed that the reaction mainly proceeds via CA direct decarboxylation, contrary to the results reported in previous studies. The findings demonstrated that the role of water can change according to the conditions and reactions employed. This was proven by the evident variation of kinetic rate constants under sub- and supercritical conditions and is reflected in the Arrhenius plot.

Hydrogen peroxide is a green propellant which apart from space propulsion is used in various industrial applications. Though hydrazine was used initially, the nature of hydrazine which is a toxic, carcinogenic and hazardous fuel resulted in various space agencies’ interest in green propellants. The essential step for high test peroxide (HTP) as a green mono propellant realization is on development of a reliable, effective, long life catalytic beds which are not affected by catalytic poisoning and impurities. In the present study, a 3D model is developed using COMSOL Multiphysics software to know the catalytic decomposition of 30% hydrogen peroxide flowing inside a 3 mm diameter 300 mm length channel. The effect of annular silver catalyst (I.D – 1.6 mm, O.D. – 2 mm, length 10 mm) on decomposition rate is studied in detail. The positioning of silver catalyst bed and number of beds increased the reaction rate with varying pressure drop. Among the variations simulated, the 4 catalyst model gives the better performance and gets decomposed to a greater extent. This model will help in the design of a micro thruster which can operate efficiently with low pressure drop.

Selective catalytic reduction (SCR) of NOx with NH3 has been widely used for NOx emission control, but commercial catalysts inevitably suffer severe deactivation in SO2-containing stack gases at low temperatures because the ammonium bisulfate (NH4HSO4, ABS) formed in SCR blocks the surface active sites. We resolve this issue by developing a TiO2-supported single-atom Mo catalyst (Mo1/TiO2) that decomposes ABS at ∼225 °C, far lower than the dew point of ABS (∼260 °C). Single Mo atoms paired with the neighboring surface Ti atoms function as Mo–Ti acid–base dual sites, which respectively adsorb the NH4+ and HSO4− of ABS. After the oxidation of NH4+ by surface lattice oxygen on the Mo sites, electrons left behind on the dual sites are localized around the Fermi level, which allows them to transfer to the adsorbed HSO4− on the Ti sites, thus releasing SO2 at low temperatures. The Mo1/TiO2 catalyst with Mo–Ti acid–base dual sites enables the decomposition of ABS at low temperatures, and thus this work provides a way to effectively control NOx emission particularly from industrial boilers.

The direct nonoxidative conversion of methane (CH4) to valuable chemicals has attracted increasing interest. However, the carbon deposition will inevitably occur due to CH4 decomposition at high temperature. Here, we report the conversion of CH4 assisted by non-thermal plasma into olefins and H2 over a Pd/CeO2 catalyst. The addition of the plasma could effectively enhance the anti-coking performance of the catalyst, facilitating the conversion of CH4. The interaction between plasma and catalyst was explored in detail. The energized electron and ions generated by plasma could interact with the adsorbed CH3 species to efficiently suppress the consequent dehydrogenation of the adsorbed CH3, accelerating the desorption of the CH3 species from the surface of the catalyst, thus reducing the amount of carbon deposition on the catalyst surface. The highly efficient catalyst assisted by plasma is effective in enhancing the CH4 conversion and suppressing the carbon deposition, which deserves to be widely applied in catalysis.