Counting d-Orbital Vacancies of Transition-Metal Catalysts for the Sulfur Reduction Reaction.

The electrocatalytic sulfur reduction reaction (SRR) would allow the production of renewable high-capacity rechargeable lithium-sulfur (Li-S) batteries using sustainable and nontoxic elemental sulfur as a cathode material, but its slow reaction rate causes a serious shuttle effect and dramatically reduces the capacity. We found that a catalyst composed of Pd nanoparticles supported by ordered mesoporous carbon (Pd/OMC) had a high reaction rate in the SRR, and a Li-S battery assembled with this catalyst had a low shuttle constant of 0.031 h-1 and a high-rate performance with a specific capacity of 1527 mAh g-1 at 0.1 C which is close to the theoretical value. The high activity of Pd/OMC with a d-orbital vacancy of 0.87 e was predicted from a volcano relationship between the d charge for the metal and the adsorption activation entropy and reaction rate for the SRR by examining Pd, Au, Pt, Rh, and Ru transition-metal nanocatalysts. The strategy of using a single electronic structure descriptor to design high-efficiency SRR catalysts has suggested a way to produce practical Li-S batteries.

Turn the potential greenhouse gases into biomass in harmful algal blooms waters: A microcosm study.

Carbon sources are a critical requirement for the proliferation of algae and the occurrence of harmful algal blooms (HABs), but are often turned into methane (CH4) after the collapse of severe HABs. Here, we attempt to remove HABs, reduce algal-derived CH4 emissions, and repair the broken carbon biogeochemical cycle in aquatic systems using an integrated ecological approach including flocculation, capping, and submerged macrophyte induction, preliminary at a microcosm scale. This strategy sustainably reached 98% algal removal after 65 days of incubation and resulted in an aerobic microenvironment (ORP = +12 mv) at the sediment-water interface. The approach contributed to an approximate 60% decline in CH4 released from the aquatic environment into the atmosphere jointly through assimilation of mineralized organic carbon by submerged macrophytes, production of carbon dioxide (CO2) under aerobic conditions, and aerobic CH4 oxidation. Some of the CO2 produced in the aquatic phase contributed to inorganic carbon and formed the submerged macrophytes biomass. A combination of flocculation, capping, and submerged macrophyte incubation were significant contributors to altering the carbon budget and sealing nearly 99% of the carbon in the simulated ecosystem (the majority in sediment, followed by submerged macrophytes), providing a sustainable way to reuse algal-derived carbon and reduce CH4 emissions.