Conducting polymer hydrogels emerge as a novel class of polymeric materials that show great potential in many energy, environmental, and biomedical devices. We describe here for the first time a general supramolecular approach toward controlled in situ synthesis of one-dimensional nanostructured conductive hydrogels (polypyrrole (PPy) as a model system) using a rational dopant counterion, which is a disc-shaped liquid crystal molecular copper phthalocyanine-3,4',4″,4‴-tetrasulfonic acid tetrasodium salt (CuPcTs). The dopant molecule CuPcTs cross-linked the PPy chains to form a three-dimensional network that gelated into a hydrogel. The PPy hydrogel could be synthesized in bulk quantities with uniform morphology of self-assembled interconnected nanofibers. The tetra-functional dopant favors a supramolecular self-assembly mechanism to form one-dimensional PPy nanostructures. Furthermore, the enhanced interchain charge transport of CuPcTs doped PPy resulted in greatly enhanced conductivity and pseudocapacitance compared with pristine PPy.

The atmospheric oxidation mechanism of toluene initiated by OH radical addition is investigated by quantum chemistry calculations at M06-2X, G3MP2-RAD, and ROCBS-QB3 levels and by kinetics calculation by using transition state theory and unimolecular reaction theory coupled with master equation (RRKM-ME). The predicted branching ratios are 0.15, 0.59, 0.05, and 0.14 for OH additions to ipso, ortho, meta, and para positions (forming R1-R4 adducts), respectively. The fate of R2, R4, and R1 is investigated in detail. In the atmosphere, R2 reacts with O2 either by irreversible H-abstraction to form o-cresol (36%), or by reversible recombination to R2-1OO-syn and R2-3OO-syn, which subsequently cyclize to bicyclic radical R2-13OO-syn (64%). Similarly, R4 reacts with O2 with branching ratios of 61% for p-cresol and 39% for R4-35OO-syn, while reaction of R1 and O2 leads to R1-26OO-syn. RRKM-ME calculations show that the reactions of R2/R4 with O2 have reached their high-pressure limits at 760 Torr and the formation of R2-16O-3O-s is only important at low pressure, i.e., 5.4% at 100 Torr. The bicyclic radicals (R2-13OO-syn, R4-35OO-syn, and R1-26OO-syn) will recombine with O2 to produce bicyclic alkoxy radicals after reacting with NO. The bicyclic alkoxy radicals would break the ring to form products methylglyoxal/glyoxal (MGLY/GLY) and their corresponding coproducts butenedial/methyl-substituted butenedial as proposed in earlier studies. However, a new reaction pathway is found for the bicyclic alkoxy radicals, leading to products MGLY/GLY and 2,3-epoxybutandial/2-methyl-2,3-epoxybutandial. A new mechanism is proposed for the atmospheric oxidation mechanism of toluene based on current theoretical and previous theoretical and experimental results. The new mechanism predicts much lower yield of GLY and much higher yield of butenedial than other atmospheric models and recent experimental measurements. The new mechanism calls for detection of proposed products 2,3-epoxybutandial and 2-methyl-2,3-epoxybutandial.

A novel fungi pelletization-assisted bioflocculation technology was developed for efficient algae harvesting and wastewater treatment. Microalga Chlorella vulgaris UMN235 and two locally isolated fungal species Aspergillus sp. UMN F01 and UMN F02 were used to study the effect of various cultural conditions on pelletization process for fungi-algae complex. The results showed that pH was the key factor affecting formation of fungi-algae pellet, and pH could be controlled by adjusting glucose concentration and fungal spore number added. The best pelletization happened when adding 20 g/L glucose and approximately 1.2E8/L spores in BG-11 medium, under which almost 100% of algal cells were captured onto the pellets with shorter retention time. The fungi-algae pellets can be easily harvested by simple filtration due to its large size (2-5 mm). The filtered fungi-algae pellets were reused as immobilized cells for treatment wastewaters and the nutrient removal rates of 100, 58.85, 89.83, and 62.53 % (for centrate) and 23.23, 44.68, 84.70, and 70.34% (for diluted swine manure wastewater) for ammonium, total nitrogen, total phosphorus, and chemical oxygen demand, respectively, under both 1- and 2-day cultivations. The novel technology developed is highly promising compared with current algae harvesting and biological wastewater treatment technologies in the literature.

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In recent years, as one of the most promising candidates to replace platinum-based catalysts for oxygen reduction reaction (ORR), atomically dispersed transition metal/nitrogen-doped carbon (M-N-C) materials have become a research...

The atmospheric oxidation mechanism of 1,2,4-trimethylbenzene (1,2,4-TMB) initiated by OH radicals is investigated using quantum chemistry calculations at M06-2X and ROCBS-QB3 levels. The calculations show that the initiation of the reaction is dominated by OH addition to C1, C3 and C5 to form 1,2,4-TMB-OH adducts R1, R3, and R5 with branching ratios of 0.22, 0.19, and 0.38, respectively, using ROCBS-QB3 energies. In the troposphere, the adducts react with O2 by irreversible H-abstraction to form phenolic compounds and by reversible addition to TMB-OH-O2 peroxy radicals, which will cyclize to bicyclic radicals, similar to those in benzene, toluene, and xylenes. The bicyclic radicals can further recombine with O2 to generate bicyclic peroxy and alkoxyl radicals. The bicyclic alkoxyl radicals would break the ring directly to form 1,2-dicarbonyl products and unsaturated 1,4-dicarbonyl co-products, or undergo another cyclization to form an epoxy group, followed by the ring-breakage to form 1,2-dicarbonyl products and epoxy-1,4-dicarbonyl co-products. The predicted yields of products agree reasonably with the previous experimental measurements, while considerable discrepancies also exist for the yields of nitrates, biacetyl, 4-oxo-2-pentenal, and butenedial, etc. Our mechanism also predicts a new type of epoxy-1,4-dicarbonyl compounds with a total yield of ∼0.32. The epoxy-1,4-dicarbonyl compounds have not been suggested or reported in previous studies.

Noble-metal-free catalytic hydrogenation of nitroarenes is achieved through the rational design of atomically dispersed Ni sites on N-doped porous carbon. The outstanding activity of the catalyst originates from the atomic dispersion of Ni active sites with a high Ni–N3 content.

Phonon polaritons (PhPs) have attracted significant interest in the nano-optics communities because of their nanoscale confinement and long lifetimes. Although PhP modification by changing the local dielectric environment has been reported, controlled manipulation of PhPs by direct modification of the polaritonic material itself has remained elusive. Here, chemical switching of PhPs in α-MoO 3 is achieved by engineering the α-MoO 3 crystal through hydrogen intercalation. The intercalation process is non-volatile and recoverable, allowing reversible switching of PhPs while maintaining the long lifetimes. Precise control of the intercalation parameters enables analysis of the intermediate states, in which the needle-like hydrogenated nanostructures functioning as in-plane antennas effectively reflect and launch PhPs and form well-aligned cavities. We further achieve spatially controlled switching of PhPs in selective regions, leading to in-plane heterostructures with various geometries. The intercalation strategy introduced here opens a relatively non-destructive avenue connecting infrared nanophotonics, reconfigurable flat metasurfaces and van der Waals crystals.