Dendritic nanoarchitecture imparts ZSM-5 zeolite with enhanced adsorption and catalytic performance in energy applications

The development of zeolites possessing dendritic features represents a great opportunity for the design of novel materials with applications in a large variety of fields and,in particular,in the energy sector to afford its transition towards a low carbon system.In the current work,ZSM-5 zeolite showing a dendritic3D nanoarchitecture has been synthesized by the functionalization of protozeolitic nanounits with an amphiphilic organosilane,which provokes the branched aggregative growth of zeolite embryos.Dendritic ZSM-5 exhibits outstanding accessibility arising from a highly interconnected network of radially-oriented mesopores(3-10 nm)and large cavities(20-80 nm),which add to the zeolitic micropores,thus showing a well-defined trimodal pore size distribution.These singular features provide dendritic ZSM-5 with sharply enhanced performance in comparison with nano-and hierarchical reference materials when tested in a number of energy related applications,such as VOCs(toluene)adsorption(improved capacity),plastics(low-density polyethylene)catalytic cracking(boosted activity)and hydrogen production by methane catalytic decomposition(higher activity and deactivation resistance).

Promotional effects of Sb on Pd-based catalysts for the direct synthesis of hydrogen peroxide at ambient pressure

TiO2‐supported Pd‐Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H2O2 at ambient pressure.The addition of Sb to Pd significantly enhanced catalytic performance,and a Pd50Sb catalyst showed the greatest selectivity of up to 73%.Sb promoted the dispersion of Pd on TiO2,as evidenced by transmission electron microscopy and X‐ray diffraction.X‐ray photoelectron spectroscopy indicated that the oxidation of Pd was suppressed by Sb.In addition,Sb2O3 layers were formed and partially wrapped the surfaces of Pd catalysts,thus suppressing the activation of H2 and subsequent hydrogenation of H2O2.In situ diffuse reflection infrared Fourier transform spectroscopy for CO adsorption suggested that Sb homogenously located on the surface of Pd‐Sb catalysts and isolated contiguous Pd sites,resulting in the rise of the ratio of Pd monomer sites that are favorable for H2O2 formation.As a result,the Sb modified Pd surfaces significantly enhanced the non‐dissociative activation of O2 and H2O2 selectivity.

Study on Chemisorption and Desorption of Hydrogen and Nitrogen on Ru-based Ammonia Synthesis Catalyst

The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm, just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.

Measurement of trace nitrate concentrations in seawater by ion chromatography with valve switching

An ion chromatographic method with a valve switching facility was developed to determine trace nitrate concentrations in seawater using two pumps, two different suppressors, and two columns. A carbohydrate membrane desalter was used to reduce the high concentrations of sodium salts in samples. In this method, trace nitrate was eluted from the concentrator column to the analytical columns, while the matrix fl owed to waste. Neither chemical pre-treatment nor sample dilution was required. In the optimized separation conditions, the method showed good linearity( R >0.99) in the 0.05 and 50 mg/L concentration range, and satisfactory repeatability(RSD<5%, n =6). The limit of detection for nitrate was 0.02 mg/L. Results showed that the valve switching system was suitable and practical for the determination of trace nitrate in seawater.

Analysis on Ammonia Synthesis over Wustite-Based Iron Catalyst

Wustite-based catalyst for ammonia synthesis exhibits extremely high activity and easy to reduction under a wide range of conditions. The reaction kinetics of ammonia synthesis can be illustrated perfectly by both the classical Temkin-Pyzhev and modified Temkin equations with optimized a of 0.5. The pre-exponent factors and activation energies at the pressures of 8.0 and 15.0MPa are respectively k0 = 1.09 x 1015, 7.35 X 1014Pa0.5.s-1, and E = 156.6, 155.5kJ-mol-1 derived from the classical Temkin-Phyzhev equation, as well as k0 = 2.45 X 1014, 1.83 X 1014Pa0.5s-1, and E = 147.7, 147.2kJ-mol-1 derived from the modified Temkin equation. Although the degree of reduction under isothermal condition is primarily dependent upon temperature, low pressure seems to be imperative for reduction under high temperature and low space velocity to be considered as a high activity catalyst. The reduction behavior with dry feed gas can be illustrated perfectly by the shrinking-sphere-particle model, by which the reduction-rate constants of 4248exp (-71680/KT) and 644exp (-87260/RT) were obtained for the powder (0.045-0.054mm) and irregular shape (nominal diameter 3.17 mm) catalysts respectively. The significant effect of particle size on reduction rate was observed, therefore, it is important to take into account the influence of particle size on reduction for the optimization of reduction process in industry.

Molecular Dynamics Study of Hydrogen Dissociation on Pd Surfaces using Reactive Force Fields

Developing a widely-used reactive force field is meaningful to explore the fundamental reaction mechanism on gas-surface chemical reaction dynamics due to its very high computational efficiency. We here present a study of hydrogen and its deuterated molecules dissociation on Pd surfaces based on a full-dimensional potential energy surface （PES） constructed by using a simple second moment approximation reactive force field （SMA RFF）. Although the descriptions of the adsorbate-substrate interaction contain only the dissociation reaction of H2/Pd（111） system, a good transferability of SMA potential energy surface （PES） is shown to investigate the hydrogen dissociation on Pd（100）. Our simulation results show that, the dissociation probabilities of H2 and its deuterated molecules on Pd（111） and Pd（100） surfaces keep non-monotonous variations with respect to the incident energy Ei, which is in good agreement with the previous ab initio molecular dynamics. Furthermore, for the oriented molecules, the dissociation probabilities of the oriented H2 （D2 and T2） molecule have the same orientation dependence behavior as those oriented HD （HT and DT） molecules.

Model Catalysts from Single Crystal to Nanocrystals/Nano-Composites

Heterogeneous catalysis is a key technology for chemical and materials synthesis,fuel production,power generation and conversion,and environmental remediation.To cope with resources(energy)shortage and environmental pollution,chemical processes should be not only effi cient but also clean,and catalysts must be active and selective.The innovation of such catalysts requires a fundamental understanding of the structure-activity relation of catalysts that can guide the design of catalyst structures.

Molecular catalysis for the steam reforming of ethanol

In this paper, the application of molecular catalysis for steam reforming of ethanol （SRE） is reviewed. Eight metals （Ni, Co, Cu Pt, Rh, Pd, Ir and Ru） have shown high catalytic activity for SRE. Among them Ni and Rh are very promising because of high d character in the metal bond and low metal-oxygen bonding （vs. metal-carbon）. They can effectively promote C-C bond cleavage in the rate-determining process during SRE. However, Rh is weak in water-gas-shift so that CH4 and CO become the main by-products at low reaction temperatures, while Ni catalysts suffer from rapid deactivation due to coking and sintering. Two low-temperature CO-free catalysts have been developed in our lab, namely Rh-Fe/Ca-Al2O3 and carbonyl-derived Rh-Co/CeO2, in which the presence of iron oxide or Co can promote water-gas-shift reaction and significantly improve the SRE performance. On the other hand, adding 3 wt% CaO to Ni/Al2O3 can greatly improve the catalyst stability because the Ca modification not only increases Ni concentration on the Ni/Ca-Al2O3 surface and 3d valence electron density, but also facilitates the water adsorption and coke gasification via water-gas-shift. The availability of abundant surface OH groups helps the formation and conversion of adsorbed formate intermediate. Hence, ethanol reaction on Ca-Al2O3-supported Ni, Pt, Pd and Rh catalysts are found to follow the formate-intermediated pathway, a new reaction pathway alternative to the traditional acetate-interrnediated pathway.

Towards maximized utilization of iridium for the acidic oxygen evolution reaction

The reduction in noble metal content for efficient oxygen evolution catalysis is a crucial aspect towards the large scale commercialisation of polymer electrolyte membrane electrolyzers.Since catalytic stability and activity are inversely related,long service lifetime still demands large amounts of low-abundant and expensive iridium.In this manuscript we elaborate on the concept of maximizing the utilisation of iridium for the oxygen evolution reaction.By combining different tin oxide based support materials with liquid atomic layer deposition of iridium oxide,new possibilities are opened up to grow thin layers of iridium oxide with tuneable noble metal amounts.In-situ,time-and potential-resolved dissolution experiments reveal how the stability of the substrate and the catalyst layer thickness directly affect the activity and stability of deposited iridium oxide.Based on our results,we elaborate on strategies how to obtain stable and active catalysts with maximized iridium utilisation for the oxygen evolution reaction and demonstrate how the activity and durability can be tailored correspondingly.Our results highlight the potential of utilizing thin noble metal films with earth abundant support.materials for future catalytic applications in the energy sector.

Improved oxidation of hydrogen off-gas by hydrophobic surface modification: A multiscale density functional theory study

A catalytic micro-reactor for converting hydrogen off-gas into water was recently developed, through which the conversion efficiency of hydrogen gas was greatly improved by hydrophobic modification of the catalytic substrate. Herein, a hybrid theoretical method is reported that combines density functional theory (DFT) on both the quantum and molecular scales. This method allows the microscopic study of the mechanism by which the surface catalytic reaction can be manipulated. Specifically, quantum DFT calculations are performed to quantify the molecular interaction between the catalytic substrate and reagent or product. Classical DFT investigations are subsequently carried out to determine the local concentrations of reagents near catalytic sites subject to different surface coating conditions. Finally, the reaction efficiency is determined from the local concentrations based on collision theory. This multiscale method provides molecular insight for quantifying the effect of catalytic surface modification on the reaction efficiency. The method reveals that an optimal surface hydrophobic modification can promote the densities of reagents near the substrate, while depleting the produced water. These two factors promote the conversion efficiency. The exclusion of produced water from the catalytic substrate is affected more by the degree of polymer grafting than by the chain length of hydrophobic polymer moieties.

Pettifor maps of complex ternary two-dimensional transition metal sulfides

Alloying is an established strategy to tune the properties of bulk compounds for desired applications.With the advent of nanotechnology,the same strategy can be applied to 2D materials for technological applications,like single-layer transistors and solid lubricants.Here we present a systematic analysis of the phase behaviour of substitutional 2D alloys in the Transition Metal Disulfides(TMD)family.The phase behaviour is quantified in terms of a metastability metric and benchmarked against many-body expansion of the energy landscape.We show how the metastability metric can be directly used as starting point for setting up rational search strategies in phase space,thus allowing for targeted further computational prediction and analysis of properties.The results presented here also constitute a useful guideline for synthesis of TMDs binary alloys via a range of synthesis techniques.