Promoting Surface Electric Conductivity for High-Rate LiCoO2.

The cathode materials work as the host framework for both Li+ diffusion and electron transport in Li-ion batteries. The Li+ diffusion property is always the research focus, while the electron transport property is less studied. Herein, we propose a unique strategy to elevate the rate performance through promoting the surface electric conductivity. Specifically, a disordered rock-salt phase was coherently constructed at the surface of LiCoO2 , promoting the surface electric conductivity by over one magnitude. It increased the effective voltage (Veff ) imposed in the bulk, thus driving more Li+ extraction/insertion and making LiCoO2 exhibit superior rate capability (154 mAh g-1 at 10 C), and excellent cycling performance (93 % after 1000 cycles at 10 C). The universality of this strategy was confirmed by another surface design and a simulation. Our findings provide a new angle for developing high-rate cathode materials by tuning the surface electron transport property.

Tuning the exposure of BiVO4-{010} facets to enhance the N2 photofixation performance.

Effective separation of photoexcited carriers and chemisorption of the N2 molecule are two key issues to efficient nitrogen photofixation. The spatial charge separation of BiVO4 with anisotropic exposed facets, namely the transfer of photoexcited electrons and holes to {010} and {110} facets, respectively, helps to enhance the separation ability of photogenerated carriers. Theoretical calculation results predict that a surface oxygen vacancy is easier to form on the (010) facet than on the (110) facet of BiVO4. Accordingly, in this study, enhanced N2 photofixation performance has been achieved for the first time by tuning the exposure of {010} facets of BiVO4.

Wavelength-Dependent Solar N2 Fixation into Ammonia and Nitrate in Pure Water.

Solar-driven N2 fixation using a photocatalyst in water presents a promising alternative to the traditional Haber-Bosch process in terms of both energy efficiency and environmental concern. At present, the product of solar N2 fixation is either NH4 + or NO3 -. Few reports described the simultaneous formation of ammonia (NH4 +) and nitrate (NO3 -) by a photocatalytic reaction and the related mechanism. In this work, we report a strategy to photocatalytically fix nitrogen through simultaneous reduction and oxidation to produce NH4 + and NO3 - by W18O49 nanowires in pure water. The underlying mechanism of wavelength-dependent N2 fixation in the presence of surface defects is proposed, with an emphasis on oxygen vacancies that not only facilitate the activation and dissociation of N2 but also improve light absorption and the separation of the photoexcited carriers. Both NH4 + and NO3 - can be produced in pure water under a simulated solar light and even till the wavelength reaching 730 nm. The maximum quantum efficiency reaches 9% at 365 nm. Theoretical calculation reveals that disproportionation reaction of the N2 molecule is more energetically favorable than either reduction or oxidation alone. It is worth noting that the molar fraction of NH4 + in the total product (NH4 + plus NO3 -) shows an inverted volcano shape from 365 nm to 730 nm. The increased fraction of NO3 - from 365 nm to around 427 nm results from the competition between the oxygen evolution reaction (OER) at W sites without oxygen vacancies and the N2 oxidation reaction (NOR) at oxygen vacancy sites, which is driven by the intrinsically delocalized photoexcited holes. From 427 nm to 730 nm, NOR is energetically restricted due to its higher equilibrium potential than that of OER, accompanied by the localized photoexcited holes on oxygen vacancies. Full disproportionation of N2 is achieved within a range of wavelength from ~427 nm to ~515 nm. This work presents a rational strategy to efficiently utilize the photoexcited carriers and optimize the photocatalyst for practical nitrogen fixation.