Fast pyrolysis kinetics of waste tires and its products studied by a wireless-powered thermo-balance.

Fast pyrolysis is commonly used in industrial reactors to convert waste tires into fine chemicals and fuels. However, current thermogravimetric analyzers are facing limitations that prevent the acquisition of kinetic information. To better understand the reaction kinetics, we designed a novel thermo-balance device that was capable of in-situ weight measurement during rapid heating. The results showed that the reaction rate substantially increased, with significant reductions in reaction time and apparent activation energy compared to slow pyrolysis. The change of reaction mechanism from the reaction order model to the nucleation and growth model was responsible for the increase in the degradation rate. Fast pyrolysis led to the generation of more trimers of isoprene as primary pyrolytic volatiles, which we further supported through density functional theory calculations. The findings suggested that fast pyrolysis has a higher chance of overcoming the high energy barrier to form trimers of isoprene. This comprehensive and in-depth understanding of fast pyrolysis kinetics and product distribution could reveal a more realistic process of waste pyrolysis, which benefited the industry.

All-in-one strategy to prepare molded biochar with magnetism from sewage sludge for high-efficiency removal of Cd(â ¡).

Biochar in powder could lead to the separation difficulties after using and easy dispersion by wind with non-necessary consumption during the practical application. The current method for preparing molded biochar is multi-step, tedious, and required exogenous reagents. Moreover, the dehydration of sewage sludge with high water content (>85%) causes expensive production cost, limiting its secondary utilization. Therefore, an "all-in-one" strategy was developed to prepare molded biochar with magnetism by using sewage sludge as endogenetic binder, water source, carbon source, as well as magnetic source, and biomass wastes as water moderator and pore-forming agent. The molded biochar showed high removal capacity towards Cd(Ⅱ) of 456.2 mg/g, which was 6 times higher than the commercial activated carbon in powder (69.1 mg/g). The excellent removal performance of the molded biochar was in linear correlation the O/C ratio (R2 =0.855), resulting in the complexation with Cd(Ⅱ). DFT calculations indicated the amounts and species of oxygen changed the electron distribution and electron-donation properties of biochar for Cd(Ⅱ). Moreover, the Na+ exchanges with Cd(Ⅱ) were also an important removal mechanism. This study provided a novel synthesis strategy for the molded biochar with both high particle density and high adsorption capability.

A room-temperature formaldehyde sensor based on hematite for breast cancer diagnosis.

Formaldehyde (HCHO) is regarded as one kind of indoor pollutant. Additionally, HCHO serves as a biomarker in the exhaled breath of breast cancer patients. Early warning and management are crucial for the environment and human health. Thus, we have elaborately synthesized hematite (α-Fe2O3) employing a facet-engineering hydrothermal strategy using the fine-tuned solvent composition, with special attention to the effect of different exposed surfaces on HCHO detection. The spindle-like α-Fe2O3 nanocrystals with the (012) facet exposed exhibited impressively higher response towards HCHO at room temperature than that of the disk-like α-Fe2O3 with mainly the (001) facet exposed, partly due to the abundant vacancy oxygen and adsorbed oxygen of high-index facets of α-Fe2O3. More importantly, our experimental results coincide with theoretical calculations. Overall, the surface engineering strategy could be extended to a versatile approach for HCHO detection.

Comparison of Vitamin C and Its Derivative Antioxidant Activity: Evaluated by Using Density Functional Theory.

Vitamin C (VC) is an essential antioxidant, but its application is limited because of its unstable chemical properties. Hence, a variety of VC derivatives have emerged in practical antioxidant applications. To explore the relationship between the antioxidant properties and the chemical structures of vitamin C and its derivatives, density functional theory (DFT) was used in this work to calculate the reaction enthalpies of the mechanisms related to radical scavenging activity. The structures were optimized at the B3LYP-D3(BJ)/6-31G* level of theory. Single point calculations (SPE) were performed at the PWPB95-D3 (BJ)/def2-QZVPP level. To estimate the solvent effect on antioxidant properties, the SMD (solvation model based on density) method was used. The results showed that in the process of optimizing the chemical structure of vitamin C, the antioxidant capacity of its derivatives decreased slightly in aqueous solvents. In the calculation process, it is also found that in the choice of antioxidant mechanism, these compounds are more inclined to the hydrogen atom transfer (HAT) mechanism, and from the chemical structure point of view, the double bond of the lactone ring is essential for its free radical scavenging activity. In general, it is necessary to continue to optimize the structure of VC to obtain derivatives with better oxidation resistance and more practical value.

Density functional theory-based investigation of HCN and NH3 formation mechanisms during phenylalanine pyrolysis.

As sludge pyrolysis produces large amounts of toxic NH3 and HCN, many works have studied nitrogen transfer during this process, commonly employing amino acids as models of sludge protein. Herein, density functional theory is used to probe the production of HCN and NH3 during the pyrolysis of phenylalanine as a model, revealing the existence of two formation paths for each gas. In the first (lower-energy-barrier) NH3 formation path, the hydrogen bonding-assisted transfer of carboxyl group hydrogen to the amino group is followed by direct NH3 generation via decarboxylation, and the second (higher-energy-barrier) path features decarboxylation followed by the transfer of carboxyl group hydrogen to the adjacent carbon atom to form phenethylamine, the deamination of which affords NH3 and styrene. For HCN, the first (lower-energy-barrier) path features C2-C3 bond cleavage to afford dehydroglycine, which further decomposes to produce HCN, while in the second path, the decomposition of phenylalanine into phenethylamine, CO, and H2O is followed by internal hydrogen transfer in phenethylamine to generate HCN. The overall energy barrier of the two HCN formation paths exceeds that of NH3 formation paths, i.e., phenylalanine is more prone to afford NH3 than HCN upon pyrolysis.