Abstract
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.
Highlights
Ammonia (NH3) and nitrate are widely used for agricultural and chemical synthesis purposes [1,2,3,4]
The scanning electron microscopy (SEM) images indicate that the as-synthesized W18O49 consists of ultrathin nanowires (Figure 1(b)), while the transmission electron microscopy (TEM) image (Figure 1(c)) further confirms that the diameters and the lengths of the as-synthesized nanowires are 2 μm, respectively
The selected area electron diffraction (SAED) pattern demonstrates that the diffraction rings belong to the (010, 020) planes of the W18O49 structure (inset in Figure 1(c)), consistent with X-ray diffraction (XRD)
Summary
Ammonia (NH3) and nitrate are widely used for agricultural and chemical synthesis purposes [1,2,3,4]. Either NH4+ or NO3- as a solar N2 fixation product has been reported based on a tungsten oxide photocatalyst [8, 14], in which only the photogenerated electrons or holes are utilized. The N≡N triple bond can be weakened and activated when electrons are injected from the solid-state catalysts into the empty antibonding π∗-orbitals of the nitrogen molecule [8, 18] For this purpose, abundant active sites with localized electrons should be created so that the N2 molecule can be chemisorbed for facile electron access. A mechanism for wavelength-controlled N2 fixation via its simultaneous reduction and oxidation on defected surfaces was proposed, which sheds new light on the understanding of photocatalytic nitrogen fixation with different product selectivity and could provide guidelines for the design of future photocatalysts with higher utilization efficiency of photoexcited carriers
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