Effect of Desorption Damage on the Kinetic Characteristics of Coal Particle Gas Desorption.

There is a positive feedback mechanism of desorption, pulverization, and redesorption in the process of coal and gas outburst. The coal pore structure changes to some extent in the process of coal pulverization and has a related impact on the dynamic parameters of coal particle gas desorption. To understand the impact of desorption damage on the dynamic characteristics of coal particle gas desorption, in this paper, a self-developed coal particle gas desorption test device is used to measure the amount of methane desorption of different coal samples repeatedly desorbed under the same adsorption equilibrium pressure. The results show that the methane desorption kinetic curves of the four coal samples based on desorption damage basically have the same trend. Nie's diffusion model can better describe the methane desorption characteristics of coal particles. After desorption, the methane desorption amount, initial desorption velocity, diffusion ability, and ultimate amount of methane desorption of the coal samples are greater than those before desorption. The desorption damage affects the relevant dynamic parameters of the coal particle gas diffusion model, and its impact on the outburst coal is greater than that on raw coal. In addition, the pore size distribution and change characteristics of the coal samples before and after desorption are analyzed quantitatively via a low-temperature liquid nitrogen adsorption test and fractal dimension-related theory. It was found that the pore volume peak area of the coal samples affected by desorption damage within each pore size range was significantly larger than that before desorption. Among them, micropores have the most significant impact on the desorption damage of coal samples, and the peak area of the pore volume of protruding coal is greater than that of raw coal, indicating that the internal pores of coal after desorption damage are more developed than those of raw coal.

Electronic and Potential Synergistic Effects of Surface-Doped P-O Species on Uniform Pd Nanospheres: Breaking the Linear Scaling Relationship toward Electrochemical Oxygen Reduction.

Developing efficient oxygen reduction reaction (ORR) electrocatalysts is critical to fuel cells and metal-oxygen batteries, but also greatly hindered by the limited Pt resources and the long-standing linear scaling relationship (LSR). In this study, ∼6 nm and highly uniform Pd nanospheres (NSs) having surface-doped (SD) P-O species are synthesized and evenly anchored onto carbon blacks, which are further simply heat-treated (HT). Under alkaline conditions, Pd/SDP-O NSs/C-HT exhibits respective 8.7 (4.3)- and 5.0 (5.5)-fold enhancements in noble-metal-mass- and area-specific activity (NM-MSA and ASA) compared with the commercial Pd/C (Pt/C). It also possesses an improved electrochemical stability. Besides, its acidic ASA and NM-MSA are 2.9 and 5.1 times those of the commercial Pd/C, respectively, and reach 65.4 and 51.5% of those of the commercial Pt/C. Moreover, it also shows nearly ideal 4-electron ORR pathways under both alkaline and acidic conditions. The detailed experimental and theoretical analyses reveal the following: (1) The electronic effect induced by the P-O species can downshift the surface d-band center to weaken the intermediate adsorptions, thus preserving more surface active sites. (2) More importantly, the potential hydrogen bond between the O atom in the P-O species and the H atom in the hydrogen-containing intermediates can in turn stabilize their adsorptions, thus breaking the ORR LSR toward more efficient ORRs and 4-electron pathways. This study develops a low-cost and high-performance ORR electrocatalyst and proposes a promising strategy for breaking the ORR LSR, which may be further applied in other electrocatalysis.