Surface chemistry and kinetics of the hydrolysis of isocyanic acid on anatase

In order to meet the stricter NO_x and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO₂. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 °C the reaction was in the intrinsic kinetic regime (E_A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH₃ and NO₂, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO₂ were most effective in blocking cations and anions of TiO₂. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO₂ forms Ti–NCO and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH₃ and NO₂ retards hydrolysis leading to the appearance of isocyanate species on the surface.     

Ribosome display of mammalian receptor domains

Many mammalian receptor domains, among them a large number of potential therapeutic target proteins, are highly aggregation-prone upon heterologous expression in bacteria. This severely limits functional studies of such receptor domains and also their engineering towards improved properties. One of these proteins is the Nogoreceptor, which plays a central role in mediating the inhibition of axon growth and functional recovery after injury of the adult mammalian central nervous system. We show here that the ligand binding domain of the Nogoreceptor folds to an active conformation in ternary ribosomal complexes, as formed in ribosome display. In these complexes the receptor is still connected, via a C-terminal tether, to the peptidyl tRNA in the ribosome and the mRNA also stays connected. The ribosome prevents aggregation of the protein, which aggregates as soon as the release from the ribosome is triggered. In contrast, no active receptor was observed in phage display, where aggregation appears to prevent incorporation of the protein into the phage coat. This strategy sets the stage for rapidly studying defined mutations of such aggregation-prone receptors in vitro and to improve their properties by in vitro evolution using the ribosome display technology.     

Elastic properties of adhesive polymers. II. Polymer films and bond lines by means of nanoindentation

Seven different polymers used frequently as adhesives and/or matrix polymers in wood, wood composites, and natural fiber‐reinforced composites were studied by uniaxial tensile tests and nanoindentation. It was shown that the elastic modulus, the hardness, the creep factor, and the elastic‐, plastic‐, and viscoelastic work of indentation of the seven different polymers is essentially the same regardless whether the polymers were tested in the form of pure films or in situ, i.e., in an adhesive bond line with spruce wood. An excellent correlation was found between the elastic modulus measured by tensile tests and the elastic modulus measured by nanoindentation. In spite of the good correlation, the elastic modulus measured by nanoindentation is significantly higher than the elastic modulus measured by tensile tests. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1234–1239, 2006     

Novel biocatalysts: Recent developments

The limited number of suitably well characterized biocatalysts continues to limit progress in the application of biological routes in the synthesis of compounds for novel pharmaceuticals, materials, or performance chemicals. In this situation, the discovery of novel biocatalysts or novel functionalities or substrates on existing ones is an important task. This work describes a range of novel biocatalysts obtained recently through one of three techniques: environmental sampling or screening, protein engineering on existing enzymes, or extension of the catalytic profile of existing catalysts.     

基于不同三组分模型解析生物质热解过程

三组分模型（three pseudocomponent model）通常被用来表征生物质热解过程。传统三组分模型中单个模型的反应级数被限定为1或3。在本研究过程中，利用非线性最小二乘法，在不限定反应级数的前提下回归三组分模型动力学参数（活化能、指前因子、反应级数）。通过研究发现，纤维素（cellulose）分解反应级数接近1，与前人结果相一致。木质素（lignin）分解级数与生物质种类有关，接近于1或3。半纤维素（hemicellulose）的分解过程最复杂，其反应级数在1.5～4之间变化。以Ozawa方法计算得到的活化能作为相对标准，对3种三组分模型进行比较，发现反应级数未确定时的模型比其他两种模型更精确地表征生物质热解过程。     

Modulation of silica layer properties by varying the granulometric state of tetraethyl orthosilicate precursor aerosols during combustion chemical vapor deposition (CCVD)

Abstract

For the purpose of silica surface layer modulation, a pneumatic-controlled two-substance atomizer with inertia-based coarse droplet separation was operated at different system pressures for tetraethyl orthosilicate precursor aerosol supply during combustion chemical vapor deposition. A comprehensive testing study was performed to characterize the atomizer’s performance characteristics, initial precursor aerosols at the atomizer’s outlet, transformed aerosols before combustion, combustion aerosols and formed layers. Laser diffraction spectrometry, differential electrical mobility analyses and condensation particle counting were used for aerosol characterization with regard to particle size and particle production quantities. Layers were characterized by scanning electron microscopy, atomic force microscopy, spectral ellipsometry, water contact angle measurements and light transmission concerning geometric properties (thickness, surface structure and roughness) and physical behaviors (i.e., optical behaviors, hydrophobicity). Results show a quasi-linear relationship of the ejection mass flow of the pneumatic-controlled atomizer and geometric layer properties which again show a direct relationship to the physical properties. No correlation was found between the aerosols before combustion and the combustion aerosols since the majority of combustion aerosol particles are synthesized solely from the gas phase based on evaporated precursor material.

Copyright © 2020 American Association for Aerosol Research     

Temporal and spatial dynamics of surface run‐off from Lake Basaka catchment (Ethiopia) using SCS‐CN model coupled with remote sensing and GIS

The Lake Basaka catchment (Ethiopia) has undergone a significant land use–land cover (LULC) change and lake level rise over the past five decades. Significant quantities of water and sediment flow annually into the lake through erosion processes. An appropriate method of estimating the surface run‐off from such ungauged and dynamic catchment is extremely important for delineating sensitive areas (based on run‐off responses) to be protected and for development of suitable measures to reduce run‐off and associated soil loss. Reliable prediction of run‐off, however, is very difficult and time‐consuming for catchments such as that of Lake Basaka. The present study estimated the dynamics of surface (direct) run‐off using the NRCS‐CN model in ArcGIS, assisted by remote sensing and ancillary data. The results indicated the Lake Basaka catchment experienced significant temporal and spatial variability in its run‐off responses, depending on the rainfall (amount and distribution) pattern and LULC changes. A significant run‐off increase occurred after 1973, consistent with significant LULC changes and lake level increments occurring after that period. A reduced vegetation cover also resulted in increased run‐off coefficient of the lake catchment from 0.11 in the 1970s to 0.23 in the 2000s, indicating the important need to consider possible future LULC evolution when forecasting the lake catchment run‐off behaviour.     

Hydroisomerization of Renewable and Fossil n-Alkanes over Bifunctional Dealuminated ZSM-5 Catalysts

The hydroisomerization of two long-chain n-alkane mixtures was investigated over bifunctional Pt/H-ZSM-5 catalysts before and after dealumination of preshaped zeolite/binder pellets. The hydroisomerization over the dealuminated catalysts leads to more isomers and less cracking products. Consequently, higher ratios of multi- to mono-branched isomerization products are formed as expected for large- rather than medium-pore zeolites. This indicates a higher availability of space in the vicinity of the active sites and provides an attractive route to make medium-pore zeolites suitable for upgrading higher boiling hydrocarbon feeds.     

Recovery of Phosphoric Acid from Spent Petrochemical Catalysts

Petrochemical catalysts are widely used in the industry. For the production of cumene, zeolite-based catalysts containing phosphoric acid are applied. Over the time, coking deactivates the surface, and the catalyst has to be exchanged and disposed of. Different process approaches for recycling the phosphoric acid-containing catalysts were investigated. Related preliminary investigations have shown that calcination of the used catalyst is necessary prior to reprocessing. By digesting the catalyst with hydrofluoric acid, ∼96 % phosphate was recovered. However, this process is very costly in terms of process technology. More promising is digestion by basic or acidic routes. Several options are possible here, and digestion with H₃PO₄ proved to be particularly suitable. Here, phosphate yields reached up to 98.8 %, with a positive balance of economic efficiency at the same time. The catalyst can be produced and recycled in the same plant with the same reagents, what constitutes a major breakthrough towards sustainability in industrial catalysis.