Ir(CO)2(acac)] in the pores of N a Y zeolite was treated in CO and converted into [Ir4(CO)12]. The zeoliteencaged [Ir4(C0) 121 was characterized by infrared and extended X-ray absorption fine structure spectroscopies, with the data indicating a n average Ir-Ir coordination number of 2.6 and a n average Ir-Ir distance of 2.69 A, in agreement, within the experimental error, with the published crystallographic data for solid [Ir4(C0)12]. Structurally simple zeolite-encaged iridium clusters were made by decarbonylation of the [Ir4(CO)12] a t 325 O C in flowing He followed by Hz. The decarbonylated clusters had an average Ir-Ir coordination number of 3.4 and a bond distance of 2.70 A, consistent with the inference that the tetrahedral framework structure of [Ir4(C0) 121 had been retained after decarbonylation; thus, the cluster is represented as tetrahedral Ir4. Infrared spectra showed that [Ir4(CO)12] was re-formed when the sample was treated in CO at 60 O C .
For resource reutilization, scrap tyres have long been investigated as an additive to concrete to form 'Rubcrete' for various applications and have shown promising results. However, the addition of rubber particles leads to the degradation of physical properties, particularly, the compressive strength of the concrete. In this study, a theoretical model was proposed to shed light on the mechanisms of decrease in compressive strength due to the addition of rubber particles as well as improvement in compressive strength through modification of particle surfaces. The literature suggests that the compressive strength can be improved by soaking the rubber particles in alkaline solution first to increase the inter-phase bonding between the rubber particles and cement. Instead, we discovered that the loss in compressive strength was due to local imperfections in the hydration of cement, induced by the addition of heterogeneous and hydrophobic rubber particles. Microscopic studies showed that the rubber particles disturbed the water transfer to create channels, which were prone to cracking and led to a loss in the compressive strength. Unexpectedly, no cracking was found along the surfaces of the rubber particles, indicating that the bonding strength between the rubber particles and cement phases was not the critical factor in determining the compressive strength. Therefore, a theoretical model was proposed to describe the water transfer in the Rubcrete specimens to explain the experimental data. In the model, the local water available for hydration (Q) is: Q = -A(slv)/6piv, where Q, A(slv), and v are mass flow rate (kg s(-1)), Hamaker constant (J), and dynamic viscosity (m2 s(-1)), respectively. By maximizing the quantity Q and, in turn, the Hamaker constant A(slv), the compressive strength could be improved. The Hamaker constant A(slv) for water film on rubber particle surfaces was smaller than that for the hydrated cement particles; the water transfer rate was lower in the presence of rubber particles because the Hamaker constant A(slv) for water film on rubber particle surfaces was smaller than that on the hydrated cement particles. Thus, the compressive strength of Rubcrete could be improved by increasing the Hamaker constant of the system. This was achieved by increasing the refractive indices of the solids (n(s)). The refractive indices of materials increase with increases in functional groups, such as OH and SH on the surface. The model provided a possible mechanism for the efficacy of treating rubber particles with NaOH in improving the compressive strength. By using NaOH solution treatment, an oxygen-containing OH group was formed on the rubber surface to increase the Hamaker constant of the system, leading to higher compressive strength. Based on this mechanism, a novel method for modification of the rubber particles was also proposed. In this process, the rubber particles were partially oxidized with hot air/steam in a fluidized bed reactor to produce the hydrophilic groups on the surface of the particles. Pre...
Refractory pollutants, including lignin, tannic acid, chlortetracycline, and EDTA, were destroyed by an electrochemical oxidation method to evaluate the applicability of this method for industrial wastewater pretreatment. Operation parameters, such as supporting electrolyte, current density, and electrolyte concentration, have been investigated for their influences on COD removal efficiencies during electrolysis. In addition, gel permeation chromatography (GPC), Microtox test, and total organic halogen (TOX) analyses were performed to monitor the changes of organic characteristics of these refractory pollutants. Experimental results show that, among sulfate, nitrate, and chloride, chloride was the best supporting electrolyte, and during electrolysis, both COD and color removal efficiencies were improved by increasing current density and chloride concentration. From GPC analysis results, the electrochemical oxidation process readily destroys high-molecular-weight (HMW) organics. Microtox test results also show that the process can reduce the toxicity of these refractory organic compounds. In addition, TOX concentrations were found to increase at the beginning but then decline during the electrolysis. The above results suggest that the electrochemical oxidation process, which has good efficacy for detoxification and destruction of refractory pollutants, is a promising method for wastewater pretreatment.
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