Adsorption Mechanism and Kinetic Characterization of Bituminous Coal under High Temperatures and Pressures in the Linxing-Shenfu Area

The majority of coalbed methane(CBM) in coal reservoirs is in adsorption states in coal matrix pores. To reveal the adsorption behavior of bituminous coal under high-temperature and high-pressure conditions and to discuss the microscopic control mechanism affecting the adsorption characteristics, isothermal adsorption experiments under hightemperature and high-pressure conditions, low-temperature liquid nitrogen adsorption-desorption experiments and CO2 adsorption experiments were performed on coal samples. Results show that the adsorption capacity of coal is comprehensively controlled by the maximum vitrinite reflectance(Ro, max), as well as temperature and pressure conditions. As the vitrinite reflectance increases, the adsorption capacity of coal increases. At low pressures, the pressure has a significant effect on the positive effect of adsorption, but the effect of temperature is relatively weak. As the pressure increases, the effect of temperature on the negative effect of adsorption gradually becomes apparent, and the influence of pressure gradually decreases. Considering pore volumes of pores with diameters of 1.7-100 nm, the peak volume of pores with diameters 10-100 nm is higher than that from pores with diameters 1.7-10 nm, especially for pores with diameters of 40-60 nm, indicating that pores with diameters of 10-100 nm are the main contributors to the pore volume. The pore specific surface area shows multiple peaks, and the peak value appears for pore diameters of 2-3 nm, indicating that this pore diameter is the main contributor to the specific surface area. For pore diameters of 0.489-1.083 nm, the pore size distribution is bimodal, with peak values at 0.56-0.62 nm and 0.82-0.88 nm. The adsorption capability of the coal reservoir depends on the development degree of the supermicroporous specific surface area, because the supermicroporous pores are the main contributors to the specific pore area. Additionally, the adsorption space increases as the adsorption equilibrium pressure increases. Under the same pressure, as the maximum vitrinite reflectance increases, the adsorption space increases. In addition, the cumulative reduction in the surface free energy increases as the maximum vitrinite reflectance increases. Furthermore, as the pressure increases, the surface free energy of each pressure point gradually decreases, indicating that as the pressure increases, it is increasingly difficult to adsorb methane molecules.

Engineering nanoporous and solid core-shell architectures of lowplatinum alloy catalysts for high power density PEM fuel cells

Low-platinum(Pt)alloy catalysts hold promising application in oxygen reduction reaction(ORR)electrocatalysis of protonexchange-membrane fuel cells(PEMFCs).Although significant progress has been made to boost the kinetic ORR mass activity at low current densities in liquid half-cells,little attention was paid to the performance of Pt-based catalysts in realistic PEMFCs particularly at high current densities for high power density,which remains poorly understood.In this paper,we show that,regardless of the kinetic mass activity at the low current density region,the high current density performance of the low-Pt alloy catalysts is dominantly controlled by the total Pt surface area,particularly in low-Pt-loading H_(2)–air PEMFCs.To this end,we propose two different strategies to boost the specific Pt surface area,the post-15-nm dealloyed nanoporous architecture and the sub-5-nm solid core–shell nanoparticles(NPs)through fluidic-bed synthesis,both of which bring in comparably high mass activity and high Pt surface area for large-current-density performance.At medium current density,the dealloyed porous NPs provide substantially higher H_(2)–air PEMFC performance compared to solid core–shell catalysts,despite their similar mass activity in liquid half-cells.Scanning transmission electron microscopy images combined with electron energy loss spectroscopic imaging evidence a previously unreported“semi-immersed nanoporous-Pt/ionomer”structure in contrast to a“fully-immersed core–shellPt/ionomer”structure,thus favoring O_(2) transport and improving the fuel cell performance.Our results provide new insights into the role of Pt nanostructures in concurrently optimizing the mass activity,Pt surface area and Pt/Nafion interface for high power density fuel cells.