Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.

Title Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.
Authors M. Favaro; F.F. Abdi; M. Lamers; E.J. Crumlin; Z. Liu; R. van de Krol; D.E. Starr
Journal J Phys Chem B
DOI 10.1021/acs.jpcb.7b06942
Abstract

Bismuth vanadate has recently drawn significant research attention as a light-absorbing photoanode due to its performance for photoelectrochemical water splitting. In this study, we use in situ ambient pressure X-ray photoelectron spectroscopy with "tender" X-rays (4.0 keV) to investigate a polycrystalline bismuth vanadate (BiVO4) electrode in contact with an aqueous potassium phosphate (KPi) solution at open circuit potential under both dark and light conditions. This is facilitated by the creation of a 25 to 30 nm thick electrolyte layer using the "dip-and-pull" method. We observe that under illumination bismuth phosphate forms on the BiVO4 surface leading to an increase of the surface negative charge. The bismuth phosphate layer may act to passivate surface states observed in photoelectrochemical measurements. The repulsive interaction between the negatively charged surface under illumination and the phosphate ions in solution causes a shift in the distribution of ions in the thin aqueous electrolyte film, which is observed as an increase in their photoelectron signals. Interestingly, we find that such changes at the BiVO4/KPi electrolyte interface are reversible upon returning to dark conditions. By measuring the oxygen 1s photoelectron peak intensities from the phosphate ions and liquid water as a function of time under dark and light conditions, we determine the time scales for the forward and reverse reactions. Our results provide direct evidence for light-induced chemical modification of the BiVO4/KPi electrolyte interface.

Citation M. Favaro; F.F. Abdi; M. Lamers; E.J. Crumlin; Z. Liu; R. van de Krol; D.E. Starr.Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.. J Phys Chem B. 2017. doi:10.1021/acs.jpcb.7b06942

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Bismuth

See more Bismuth products. Bismuth (atomic symbol: Bi, atomic number: 83) is a Block P, Group 15, Period 6 element with an atomic radius of 208.98040. The number of electrons in each of Bismuth's shells is 2, 8, 18, 32, 18, 5 and its electron configuration is [Xe] 4f14 5d10 6s2 6p3. Bismuth Bohr ModelThe bismuth atom has a radius of 156 pm and a Van der Waals radius of 207 pm. In its elemental form, bismuth is a silvery white brittle metal. Bismuth is the most diamagnetic of all metals and, with the exception of mercury, its thermal conductivity is lower than any other metal. Elemental BismuthBismuth has a high electrical resistance, and has the highest Hall Effect of any metal (i.e., greatest increase in electrical resistance when placed in a magnetic field). Bismuth is found in bismuthinite and bismite. It is also produced as a byproduct of lead, copper, tin, molybdenum and tungsten extraction. Bismuth was first discovered by Early Man. The name Bismuth originates from the German word 'wissmuth,' meaning white mass.

Phosphorus

Phosphorus Bohr ModelSee more Phosphorus products. Phosphorus (atomic symbol: P, atomic number: 15) is a Block P, Group 15, Period 3 element. The number of electrons in each of Phosphorus's shells is 2, 8, 5 and its electronic configuration is [Ne] 3s2 3p3. The phosphorus atom has a radius of 110.5.pm and its Van der Waals radius is 180.pm. Phosphorus is a highly-reactive non-metallic element (sometimes considered a metalloid) with two primary allotropes, white phosphorus and red phosphorus its black flaky appearance is similar to graphitic carbon. Compound forms of phosphorus include phosphates and phosphides. Phosphorous was first recognized as an element by Hennig Brand in 1669 its name (phosphorus mirabilis, or "bearer of light") was inspired from the brilliant glow emitted by its distillation.

Potassium

Elemental PotassiumSee more Potassium products. Potassium (atomic symbol: K, atomic number: 19) is a Block S, Group 1, Period 4 element with an atomic weight of 39.0983. The number of electrons in each of Potassium's shells is [2, 8, 8, 1] and its electron configuration is [Ar] 4s1. The potassium atom has a radius of 227.2 pm and a Van der Waals radius of 275 pm. Potassium was discovered and first isolated by Sir Humphrey Davy in 1807. Potassium is the seventh most abundant element on earth. It is one of the most reactive and electropositive of all metals and rapidly oxidizes. As with other alkali metals, potassium decomposes in water with the evolution of hydrogen because of its reacts violently with water, it only occurs in nature in ionic salts.Potassium Bohr Model In its elemental form, potassium has a silvery gray metallic appearance, but its compounds (such as potassium hydroxide) are more frequently used in industrial and chemical applications. The origin of the element's name comes from the English word 'potash,' meaning pot ashes, and the Arabic word qali, which means alkali. The symbol K originates from the Latin word kalium.

Vanadium

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