Hybrid Double Perovskite Derived Halides Based on Bi and Alkali Metals (K, Rb): Diverse Structures, Tunable Optical Properties and Second Harmonic Generation Responses.

Double perovskites (DP) have attracted extensive attention due to their rich structures and wide application prospects in the field of optoelectronics. Here, we report 15 new Bi-based double perovskite derived halides with the general formula of A2 BBiX6 (A=organic cationic ligand, B=K or Rb, X=Br or I). These materials are synthesized using organic ligands to coordinate with metal ions with a sp3 oxygen, and diverse structure types have been obtained with distinct dimensionalities and connectivity modes. The optical band gaps of these phases can be tuned by changing the halide, the organic ligand and the alkali metal, varying from 2.0 to 2.9 eV. The bromide phases exhibit increasing photoluminescence (PL) intensity with decreasing temperature, while the PL intensity of iodide phases changes nonmonotonically with temperature. Because the majority of these phases are non-centrosymmetric, second harmonic generation (SHG) responses are also measured for selected non-centrosymmetric materials, showing different particle-size-dependent trends. Our findings give rise to a series of new structural types to the DP family, and provide a powerful synthetic handle for symmetry breaking.

Simultaneous partial nitrification, Anammox and nitrate-dependent Fe(II) oxidation (NDFO) for total nitrogen removal under limited dissolved oxygen and completely autotrophic conditions.

Sustainable nitrogen removal from wastewater at reduced energy and/or chemical consumptions is challenging. This paper investigated, for the first time, the feasibility of coupled partial nitrification, Anammox and nitrate-dependent Fe(II) oxidation (NDFO) for sustainable autotrophic nitrogen removal. With NH4+-N as the only nitrogen-containing compound in the influent, near-complete nitrogen removal (a total of 97.5 % with a maximal total nitrogen removal rate of 6.64 ± 2.68 mgN/L/d) was achieved in a sequencing batch reactor for a 203-d operation without organic carbon source addition and forced aeration. Anammox (predominated by Candidatus Brocadia) and NDFO bacteria (such as Denitratisoma) were successfully enriched, with total relative abundances up to 11.54 % and 10.19 %, respectively. Dissolved oxygen (DO) concentration was a key factor affecting the coupling of multi (ammonia oxidization, Anammox, NDFO, iron-reduction, etc.) bacterial communities, resulting in different total nitrogen removal efficiencies and rates. In batch tests, the optimal DO concentration was 0.50-0.68 mg/L with a maximal total nitrogen removal efficiency of 98.7 %. Fe(II) in the sludge not only competed with nitrite oxidizing bacteria for DO to prevent complete nitrification, but promoted the transcription of NarG and NirK genes (10.5 and 3.5 times higher than the group without Fe(II) addition) as indicated by the reverse transcription quantitative polymerase chain reaction (RT-qPCR), resulting in increased NDFO rate (by 2.7 times) and promoted NO2--N generated from NO3--N, which back fed the Anammox process, achieving near-complete nitrogen removal. The reduction of Fe(III) by iron-reducing bacteria (IRB) and hydrolytic and fermentative anaerobes enabled a sustainable Fe(II)/Fe(III) recycling, avoiding the need in continuous Fe(II) or Fe (III) dosage. The coupled system is expected to benefit the development of novel autotrophic nitrogen removal processes with neglectable energy and material consumptions for the treatment of wastewater with low organic carbon and NH4+-N contents in underdeveloped regions, such as decentralized rural wastewaters.

Carbon uptake bioenergetics of PAOs and GAOs in full-scale enhanced biological phosphorus removal systems.

This work analyzed, for the first time, the bioenergetics of PAOs and GAOs in full-scale wastewater treatment plants (WWTPs) for the uptake of different carbon sources. Fifteen samples were collected from five full-scale WWTPs. Predominance of different PAOs, i.e., Ca. Accumulibacter (0.00-0.49%), Tetrasphaera (0.37-3.94%), Microlunatus phosphovorus (0.01-0.18%), etc., and GAOs, i.e., Ca. Competibacter (0.08-5.39%), Defluviicoccus (0.05-5.34%), Micropruina (0.17-1.87%), etc., were shown by 16S rRNA gene amplicon sequencing. Despite the distinct PAO/GAO community compositions in different samples, proton motive force (PMF) was found as the key driving force (up to 90.1%) for the uptake of volatile fatty acids (VFAs, acetate and propionate) and amino acids (glutamate and aspartate) by both GAOs and PAOs at the community level, contrasting the previous understanding that Defluviicoccus have a low demand of PMF for acetate uptake. For the uptake of acetate or propionate, PAOs rarely activated F1, F0- ATPase (< 11.7%) or fumarate reductase (< 5.3%) for PMF generation; whereas, intensive involvements of these two pathways (up to 49.2% and 61.0%, respectively) were observed for GAOs, highlighting a major and community-level difference in their VFA uptake biogenetics in full-scale systems. However, different from VFAs, the uptake of glutamate and aspartate by both PAOs and GAOs commonly involved fumarate reductase and F1, F0-ATPase activities. Apart from these major and community-level differences, high level fine-scale micro-diversity in carbon uptake bioenergetics was observed within PAO and GAO lineages, probably resulting from their versatilities in employing different pathways for reducing power generation. Ca. Accumulibacter and Halomonas seemed to show higher dependency on the reverse operation of F1, F0-ATPase than other PAOs, likely due to the low involvement of glyoxylate shunt pathway. Unlike Tetrasphaera, but similar to Ca. Accumulibacter, Microlunatus phosphovorus took up glutamate and aspartate via the proton/glutamate-aspartate symporter driven by PMF. This feature was testified using a pure culture of Microlunatus phosphovorus stain NM-1. The major difference between PAOs and GAOs highlights the potential to selectively suppress GAOs for community regulation in EBPR systems. The finer-scale carbon uptake bioenergetics of PAOs or GAOs from different lineages benefits in understanding their interactions in community assembly in complex environment.