Design of Atomically Dispersed CoN4 Sites and Co Clusters for Synergistically Enhanced Oxygen Reduction Electrocatalysis.

Constructing dual-site catalysts consisting of atomically dispersed metal single atoms and metal atomic clusters (MACs) is a promising approach to further boost the catalytic activity for oxygen reduction reaction (ORR). Herein, a porous CoSA-AC@SNC featuring the coexistence of Co single-atom sites (CoN4) and S-coordinated Co atomic clusters (SCo6) in S, N co-doped carbon substrate is successfully synthesized by using porphyrinic metal-organic framework (Co-TPyP MOF) as the precursor. The introduction of the sulfur source creates abundant microstructural defects to anchor Co metal clusters, thus modulating the electronic structure of its surrounding carbon substrate. The synergistic effect between the two types of active sites and structural advantages, in turn, results in high ORR performance of CoSA-AC@SNC with half-wave potential (E1/2) of 0.86 V and Tafel slope of 50.17 mV dec-1. Density functional theory (DFT) calculations also support the synergistic effect between CoN4 and SCo6 by detailing the catalytic mechanism for the improved ORR performance. The as-fabricated Zn-air battery (ZAB) using CoSA-AC@SNC demonstrates impressive peak power density of 174.1 mW cm-2 and charge/discharge durability for 148 h. This work provides a facile synthesis route for dual-site catalysts and can be extended to the development of other efficient atomically dispersed metal-based electrocatalysts.

High-Density CoSe2 Sites Embedded within 2D Porous N-Doped Carbon for High-Performance Oxygen Reduction Reaction Electrocatalysis.

Designing and fabricating efficient and stable nonprecious metal-based oxygen reduction reaction (ORR) electrocatalysts is a pressing and challenging task for the pursuit of sustainable new energy devices. Herein, porous P-CoSe2@NC electrocatalysts with high-density carbon-coated CoSe2 sites were successfully fabricated based on a pyridyl-porphyrinic metal-organic framework (Co-TPyP MOF) via a molten salt-assisted synthesis method. The hierarchical pore and N-doping carbon substrate of P-CoSe2@NC promotes mass transfer and electron-transfer efficiency, which is beneficial to maximize CoSe2 site utilization. Well-designed P-CoSe2@NC exhibits efficient ORR catalytic activity with a high half-wave potential of 0.863 V and excellent catalytic stability. Meanwhile, rechargeable aqueous primary/quasi-solid-state ZABs based on a P-CoSe2@NC air cathode show a high peak power density and exceptional operating stability, catering to the demands of practical applications. The qualified performance and structure stability of the electrocatalytic system may be mainly attributed to the protection of the CoSe2 nanoparticle by the coated carbon layer. Given the rational design of the structure and the component of the electrocatalyst with enhanced ORR activity, we believe that this work has provided a reliable pathway to the development of high-performance transition-metal chalcogenides for energy-storage and -conversion devices.

Estimation of respiratory heat flows in prediction of heat strain among Taiwanese steel workers.

International Organization for Standardization 7933 standard provides evaluation of required sweat rate (RSR) and predicted heat strain (PHS). This study examined and validated the approximations in these models estimating respiratory heat flows (RHFs) via convection (C res) and evaporation (E res) for application to Taiwanese foundry workers. The influence of change in RHF approximation to the validity of heat strain prediction in these models was also evaluated. The metabolic energy consumption and physiological quantities of these workers performing at different workloads under elevated wet-bulb globe temperature (30.3 ± 2.5 °C) were measured on-site and used in the calculation of RHFs and indices of heat strain. As the results show, the RSR model overestimated the C res for Taiwanese workers by approximately 3 % and underestimated the E res by 8 %. The C res approximation in the PHS model closely predicted the convective RHF, while the E res approximation over-predicted by 11 %. Linear regressions provided better fit in C res approximation (R 2 = 0.96) than in E res approximation (R 2 ≤ 0.85) in both models. The predicted C res deviated increasingly from the observed value when the WBGT reached 35 °C. The deviations of RHFs observed for the workers from those predicted using the RSR or PHS models did not significantly alter the heat loss via the skin, as the RHFs were in general of a level less than 5 % of the metabolic heat consumption. Validation of these approximations considering thermo-physiological responses of local workers is necessary for application in scenarios of significant heat exposure.

An integrated approach to assess exposure and health-risk from polycyclic aromatic hydrocarbons (PAHs) in a fastener manufacturing industry.

An integrated approach was developed to assess exposure and health-risk from polycyclic aromatic hydrocarbons (PAHs) contained in oil mists in a fastener manufacturing industry. One previously developed model and one new model were adopted for predicting oil mist exposure concentrations emitted from metal work fluid (MWF) and PAHs contained in MWF by using the fastener production rate (Pr) and cumulative fastener production rate (CPr) as predictors, respectively. By applying the annual Pr and CPr records to the above two models, long-term workplace PAH exposure concentrations were predicted. In addition, true exposure data was also collected from the field. The predicted and measured concentrations respectively served as the prior and likelihood distributions in the Bayesian decision analysis (BDA), and the resultant posterior distributions were used to determine the long-term exposure and health-risks posed on workers. Results show that long term exposures to PAHs would result in a 3.1%, 96.7%, and 73.4% chance of exceeding the PEL-TWA (0.2 mg/m3), action level (0.1 mg/m3), and acceptable health risk (10-3), respectively. In conclusion, preventive measures should be taken immediately to reduce workers' PAH exposures.

Prioritizing factors associated with thermal stresses imposed on workers in steel and iron casting industries using the Monte Carlo simulation and sensitivity analysis.

OBJECTIVES: The aims of this study were to develop approaches for monitoring and prioritizing factors associated with thermal stresses imposed on workers in iron and steel casting industries, and to eventually purpose effective control strategies. METHODS: The whole study was completed in the furnace areas of two steel casting and two iron casting plants, where the air temperature (Ta), radiant temperature (Tr), air velocity (Va) and partial water vapor pressure (Pa) were measured continuously during two consecutive work cycles. Simultaneously, the metabolic rates (M) of all workers in the furnace area were also measured. RESULTS: Using the WBGT as an index for screening purposes, our results suggest that all furnace area workers in both types of casting plants might experience severe heat stress. The predicted heat strain (PHS) model proposed by ISO 7933 was further adopted for detailed analysis from the physiological aspect. Through use of the Monte Carlo simulation and sensitivity analysis, both M and Tr were found to be the two most important factors associated with workers' thermal hazard. Therefore, two effective control strategies were suggested, including reducing workloads of workers and reducing radiant heat transmitting from furnaces to workplace environments. CONCLUSIONS: The approach developed in the present study would be beneficial to many other industries for initiating strategies to avert the thermal hazard imposed on workers.

Evaluating the efficacy of a thermal exposure chamber designed for assessing workers' thermal hazard.

This study was conducted on a thermal exposure chamber designed for assessing workers' thermal hazard. In order to assess the efficacy of the studied chamber, three environmental conditions were selected to simulate high, middle and low thermal impact situations, with air temperatures (Ta) of 43.12, 36.23 and 25.77 masculine C, globe temperatures (Tg) of 44.41, 41.07 and 29.24 masculine C, relative humidity (RH) of 77, 59 and 39%, and air flow velocities (Va) of 1.70, 0.91 and 0.25 m/s, respectively. For the three specified thermal impact conditions, results show that the coefficients of variation (CVs) for Ta, Tg, RH and Va measured in the chamber studied were consistently less than 10%, except for Va under the low thermal impact condition (=50%). For each specified thermal impact condition, we generated 1,000 environmental combinations by using the Monte Carlo simulation approach according to the variations obtained from the four environmental factors. We directly adopted the ISO 7933 approach to estimate the allowable exposure time (AET) for each simulated environmental condition. This study yielded a range in the 95% confidence interval (95% CI) of the estimated AETs for the three specified thermal impact conditions which were consistently less than 5 min. We further conducted the sensitivity analysis to examine the effect of the four environmental factors on estimating AETs. We found Va was the least important factor in estimating AETs for any specified thermal impact condition. In conclusion, although Va was found with great variation for the chamber specified in the low thermal impact condition, the exposure chamber studied can still be regarded as a feasible one for assessing workers' thermal hazard.