Exfoliated black phosphorus (BP), as a monolayer or few-layer material, has attracted tremendous attention owing to its unique physical properties for applications ranging from optoelectronics to photocatalytic hydrogen production. Approaching intrinsic properties has been, however, challenged by chemical reactions and structure degradation of BP under ambient conditions. Surface passivation by capping agents has been proposed to extend the processing time window, yet contamination or structure damage rise challenges for BP applications. Here, we report experiments combined with first-principle calculations that address the degradation chemistry of BP. Our results show that BP reacts with oxygen in water even without light illumination. The reaction follows a pseudo-first-order parallel reaction kinetics, produces PO, PO, and PO with reaction rate constants of 0.019, 0.034, and 0.023 per day, respectively, and occurs preferentially from the P atoms locating at BP edges, which yields structural decay from the nanoflake edges in water. In addition, a negligible decay ratio (0.9 ± 0.3 mol %) and preserved photocatalytic activity of BP are observed after storage in deoxygenated water for 15 days without surface passivation under ambient light. Our results reveal the chemistry of BP degradation and provide a practical approach for exfoliation, delivery, and application of BP.

The cathodic material plays an essential role in oxygen reduction reaction for energy conversion and storage systems. Titanium dioxide, as a semiconductor material, is usually not recognized as an efficient oxygen reduction electrocatalyst owning to its low conductivity and poor reactivity. Here we demonstrate that nano-structured titanium dioxide, self-doped by oxygen vacancies and selectively exposed with the high-energy {001} facets, exhibits a surprisingly competitive oxygen reduction activity, excellent durability and superior tolerance to methanol. Combining the electrochemical tests with density-functional calculations, we elucidate the defect-centred oxygen reduction reaction mechanism for the superiority of the reductive {001}-TiO2−x nanocrystals. Our findings may provide an opportunity to develop a simple, efficient, cost-effective and promising catalyst for oxygen reduction reaction in energy conversion and storage technologies.

Azo dyes are ubiquitously used in the textile industry. These dyes need to be removed from the effluent prior to discharge to sewage due to their intense color and toxicity. In this study we investigated the use of a bioelectrochemical system (BES) to abioticlly cathodic decolorization of a model azo dye, Acid Orange 7 (AO7), where the process was driven by microbial oxidation of acetate atthe anode. Effective decolorization of AO7 at rates up to 264 +/- 0.03 mol m(-3) NCC d(-1) (net cathodic compartment, NCC) was achieved at the cathode, with concomitant energy recovery. The AO7 decolorization rate was significantly enhanced when the BES was supplied with power, reaching 13.18 +/- 0.05 mol m(-3) NCC d(-1) at an energy consumption 0.012 +/- 0.001 kWh mol(-1) AO7 (at a controlled cathode potential of -400 mV vs SHE). Compared with conventional anaerobic biological methods, the required dosage of organic cosubstrate was significantly reduced in the BES. A possible cathodic reaction mechanism for the decolorization of AO7 is suggested based on the decolorization products identified: the azo bond of AO7 was cleaved at the cathode, resulting in the formation of the colorless sulfanilic acid and 1-amino-2-naphthol.

Dissimilatory metal reducing bacteria (DMRB) are capable of extracellular electron transfer (EET) to insoluble metal oxides, which are used as external electron acceptors by DMRB for their anaerobic respiration. The EET process has important contribution to environmental remediation mineral cycling, and bioelectrochemical systems. However, the low EET efficiency remains to be one of the major bottlenecks for its practical applications for pollutant degradation. In this work, Shewanella oneidensis MR-1, a model DMRB, was used to examine the feasibility of enhancing the EET and its biodegradation capacity through genetic engineering. A flavin biosynthesis gene cluster ribD-ribC-ribBA-ribE and metal-reducing conduit biosynthesis gene cluster mtrC-mtrA-mtrB were coexpressed in S. oneidensis MR-1. Compared to the control strain, the engineered strain was found to exhibit an improved EET capacity in microbial fuel cells and potentiostat-controlled electrochemical cells, with an increase in maximum current density by approximate 110% and 87%, respectively. The electrochemical impedance spectroscopy (EIS) analysis showed that the current increase correlated with the lower interfacial charge-transfer resistance of the engineered strain. Meanwhile, a three times more rapid removal rate of methyl orange by the engineered strain confirmed the improvement of its EET and biodegradation ability. Our results demonstrate that coupling of improved synthesis of mediators and metal-reducing conduits could be an efficient strategy to enhance EET in S. oneidensis MR-1, which is essential to the applications of DMRB for environmental remediation, wastewater treatment, and bioenergy recovery from wastes.