Highly Enhanced Catalytic Stability of Copper by the Synergistic Effect of Porous Hierarchy and Alloying for Selective Hydrogenation Reaction

Supported copper has a great potential for replacing the commercial palladium-based catalysts in the field of selective alkynes/alkadienes hydrogenation due to its excellent alkene selectivity and relatively high activity. However, fatally, it has a low catalytic stability owing to the rapid oligomerization of alkenes on the copper surface. In this study, 2.5 wt% Cu catalysts with various Cu:Zn ratios and supported on hierarchically porous alumina (HA) were designed and synthesized by deposition–precipitation with urea. Macropores (with diameters of 1 μm) and mesopores (with diameters of 3.5 nm) were introduced by the hydrolysis of metal alkoxides. After in situ activation at 350 °C, the catalytic stability of Cu was highly enhanced, with a limited effect on the catalytic activity and alkene selectivity. The time needed for losing 10% butadiene conversion for Cu1Zn3/HA was ~40 h, which is 20 times higher than that found for Cu/HA (~2 h), and 160 times higher than that found for Cu/bulky alumina (0.25 h). It was found that this type of enhancement in catalytic stability was mainly due to the rapid mass transportation in hierarchically porous structure (i.e., four times higher than that in bulky commercial alumina) and the well-dispersed copper active site modified by Zn, with identification by STEM–HAADF coupled with EDX. This study offers a universal way to optimize the catalytic stability of selective hydrogenation reactions.

Review of the Effects of Supplementary Cementitious Materials and Chemical Additives on the Physical, Mechanical and Durability Properties of Hydraulic Concrete

Supplementary cementitious materials (SCMs) and chemical additives (CA) are incorporated to modify the properties of concrete. In this paper, SCMs such as fly ash (FA), ground granulated blast furnace slag (GGBS), silica fume (SF), rice husk ash (RHA), sugarcane bagasse ash (SBA), and tire-derived fuel ash (TDFA) admixed concretes are reviewed. FA (25–30%), GGBS (50–55%), RHA (15–20%), and SBA (15%) are safely used to replace Portland cement. FA requires activation, while GGBS has undergone in situ activation, with other alkalis present in it. The reactive silica in RHA and SBA readily reacts with free Ca(OH)2 in cement matrix, which produces the secondary C-S-H gel and gives strength to the concrete. SF addition involves both physical contribution and chemical action in concrete. TDFA contains 25–30% SiO2 and 30–35% CaO, and is considered a suitable secondary pozzolanic material. In this review, special emphasis is given to the various chemical additives and their role in protecting rebar from corrosion. Specialized concrete for novel applications, namely self-curing, self-healing, superhydrophobic, electromagnetic (EM) wave shielding and self-temperature adjusting concretes, are also discussed.

Esterification of cellulose with betaine using p-toluenesulfonyl chloride for the in-situ activation of betaine

A novel synthesis method was developed for betaine-modified cellulose ester using a mixed N,N-dimethylacetamide/lithium chloride solvent system; p-toluenesulfonyl chloride was used for the in-situ activation of the betaine. The influence of the reaction temperature and time, as well as the anhydroglucose unit to p-toluenesulfonyl chloride to betaine mass ratio on the degree of substitution of the product was evaluated. Increasing the proportion of betaine and p-toluenesulfonyl chloride was beneficial to the esterification reaction. The degree of substitution was 1.68 at 90 °C for 32 h with an anhydroglucose unit to p-toluenesulfonyl chloride to betaine molar ratio of 1 to 2 to 3. The physicochemical properties of the betaine-modified cellulose were closely related to the degree of substitution. Major changes in the morphologies, crystallinity, thermal properties, porosity, and the average degree of polymerization resulted from the modification. The introduction of betaine made cellulose esters thermally less stable than neat cellulose but more difficult to completely degrade. The crystalline structure of the cellulose esters was destroyed, and the products exhibited a porous nature. Dye sorption studies demonstrated that the betaine-modified cellulose holds the potential of adsorbing anionic substances, which is the premise of its application.