Generation of secondary microbial methane of high-rank coals: insights from the microbial community and carbon isotope.

Secondary microbial methane could provide a valuable energy source if it were better understood. Although coal seam is an ideal environment for investigating secondary microbial methane, there are few studies to trace the secondary microbial methane of high-rank coals. Here, we collected co-produced water samples from coalbeds in the Qinshui Basin (China) and analyzed the microbial community structure by 16S ribosomal RNA (16S rRNA) amplicon sequencing analysis. 16S rRNA sequencing demonstrated abundant methanogens in coalbeds including 6 orders (Methanobacteriales, Methanococcales, Methanofastidiosales, Methanomassiliicoccale, Methanomicrobiales, and Methanosarciniales) and 22 genera of methanogens. Superheavy DIC (δ13CDIC ranging from -4.2‰ to 34.8‰) and abundance of methanogenic microbes in co-produced water revealed the generation of secondary biogenic methane in high-rank coal seams in the Qingshui Basin. Hydrogenotrophic methanogenesis is the main pathway for secondary biogenic methane production. In deeply buried coal seams, biogenic methane is dominated by CO2 and H2 reduction methanogenesis, and in shallow buried coal seams, it may be produced synergistically by hydrocarbon degradation and hydrogenotrophic methanogenic microbes. The study discussed here is important for a better understanding of the generation of secondary microbial methane in high-rank coal.

Near-IR Emissive B-N Lewis Pair-Functionalized Anthracenes via Selective LUMO Extension in Conjugated Dimer and Polymer.

Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B-N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self-sensitized reactivity toward O2 to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the π-system of BDPA to a vinyl-substituted monomer, vinylene-bridged dimer, and a polymer with an average of 20 chromophores. The extension of π-conjugation results in largely reduced band gaps of 1.8 eV for the dimer and 1.7 eV for the polymer, the latter giving rise to NIR emission with a maximum at 731 nm and an appreciable quantum yield of 7 %. Electrochemical and computational studies reveal efficient delocalization of the lowest unoccupied molecular orbital (LUMO) along the pyridyl-anthracene-pyridyl axis, which results in effective electronic communication between BDPA units, selectively lowers the LUMO, and ultimately narrows the band gap. Time-resolved emission and transient absorption (TA) measurements offer insights into the pertinent photophysical processes. Extension of π-conjugation also slows down the self-sensitized formation of endoperoxides, while significantly accelerating the thermal release of singlet oxygen to regenerate the parent acenes.