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The photocatalytic property of Fe oxide minerals has long been considered to play an important role in shaping modern terrestrial environments. However, due to the complexity of natural settings, a precise determination of the band structure of natural goethite has not been achieved. In this work, the mineralogical characteristics of natural goethite samples obtained from Zhushan, China, were systematically studied through X-ray diffraction, transmission electron microscopy, X-ray energy dispersive spectroscopy, and X-ray fluorescence spectroscopy. Afterward, the band structure for both natural and synthetic goethite samples was determined by synchrotron-based X-ray absorption and emission spectra and photoelectron spectroscopy. The band gap of natural goethite (2.25 eV) was narrower than that of its synthetic counterpart (2.55 eV), and the valence band position of natural goethite was slightly lifted (-5.06 eV) compared to that of synthetic goethite (-5.38 eV). Al doping in natural goethite crystal, as revealed by the mineralogical tests, was the main reason that contributed to this difference. The theoretical calculation showed the narrowed band gap was caused by the contribution of Al-2p orbits at the top of the valence band. Therefore, free electrons can be created under light irradiation with a shorter wavelength. The experiments showed that natural goethite can photo-catalytically degrade methyl orange, and the degradation efficiency was better (47.5%) than that of the synthetic goethite group (31.5%). This study, for the first time, revealed the band structure and confirmed the photocatalytic properties of natural goethite, which should play an important role in surface substance evolution and elemental cycling.
Shao et al. (Wed,) studied this question.