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A principal objective of our work was to illustrate the existence of unknown trends in the E CB = f(E bg ) and the E VB = f(E bg ) behavior for certain classes of compounds that also included a set of bismuthate photocatalysts; new trends may easily be hidden within more general trends. Indeed, when the data for the bismuthates are added to data related to novel visible-lightactive (VLA) photocatalysts, the trend remains the same with high significance levels for the E VB = f(E bg ) linear correlation. Using well-known data for complex (ternary) oxides, the search for new trends in the behavior of the E CB = f(E bg ) and the E VB = f (E bg ) dependences opens up the potential to develop new VLA photocatalysts. The feasibility of new desired trends can be estimated a priori using a modern theoretical analysis of the electronic structure of targeted semiconductors; note that new trends in the behavior of E CB and E VB versus bandgap energy E BG have been established for CaBi 6 O 10 , Sr 2 Bi 2 O 5 , Sr 3 Bi 2 O 6 , and Sr 6 Bi 2 O 11 . We also re-examined earlier symmetric-type plots for a set consisting of a large number of simple (binary) and a set consisting of complex (ternary) metal oxides and find some significant differences. We herein report a novel trend in the empirical dependence of the energy positions of conduction bands (E CB ) and valence bands (E VB ) on bandgap energies (E bg ) for alkali earth metal bismuthate semiconductor photocatalysts for which we show that their dependences follow the linear functions E CB = A + BE bg and E VB = a + bE bg . However, contrary to earlier symmetric relationships of some metal oxides for which A = a = 1.23 eV, B = À 0.5, and b = 0.5 toward water splitting, the relationships found for the bismuthates show them to be asymmetric with negative slopes (B < 0, b < 0) and a converging point A = a = 4.5 eV. Also re-examined are the earlier symmetric-type plots for a set consisting of a large number of simple (binary) and a set consisting of complex (ternary) metal oxides and find some significant differences. Variations in both slopes (B < 0 and b > 0) and the converging point (1.4 eV < A = a < 2.0 eV) is demonstrated. The photoactivity of some strontium bismuthates is predicted toward the photoelectrochemical reduction of CO 2 from the novel trend in behavior of their bands' energy positions relative to their bandgap energies.
A principal objective of our work was to illustrate the existence of unknown trends in the E CB = f(E bg ) and the E VB = f(E bg ) behavior for certain classes of compounds that also included a set of bismuthate photocatalysts; new trends may easily be hidden within more general trends. Indeed, when the data for the bismuthates are added to data related to novel visible-lightactive (VLA) photocatalysts, the trend remains the same with high significance levels for the E VB = f(E bg ) linear correlation. Using well-known data for complex (ternary) oxides, the search for new trends in the behavior of the E CB = f(E bg ) and the E VB = f (E bg ) dependences opens up the potential to develop new VLA photocatalysts. The feasibility of new desired trends can be estimated a priori using a modern theoretical analysis of the electronic structure of targeted semiconductors; note that new trends in the behavior of E CB and E VB versus bandgap energy E BG have been established for CaBi 6 O 10 , Sr 2 Bi 2 O 5 , Sr 3 Bi 2 O 6 , and Sr 6 Bi 2 O 11 . We also re-examined earlier symmetric-type plots for a set consisting of a large number of simple (binary) and a set consisting of complex (ternary) metal oxides and find some significant differences. We herein report a novel trend in the empirical dependence of the energy positions of conduction bands (E CB ) and valence bands (E VB ) on bandgap energies (E bg ) for alkali earth metal bismuthate semiconductor photocatalysts for which we show that their dependences follow the linear functions E CB = A + BE bg and E VB = a + bE bg . However, contrary to earlier symmetric relationships of some metal oxides for which A = a = 1.23 eV, B = À 0.5, and b = 0.5 toward water splitting, the relationships found for the bismuthates show them to be asymmetric with negative slopes (B < 0, b < 0) and a converging point A = a = 4.5 eV. Also re-examined are the earlier symmetric-type plots for a set consisting of a large number of simple (binary) and a set consisting of complex (ternary) metal oxides and find some significant differences. Variations in both slopes (B < 0 and b > 0) and the converging point (1.4 eV < A = a < 2.0 eV) is demonstrated. The photoactivity of some strontium bismuthates is predicted toward the photoelectrochemical reduction of CO 2 from the novel trend in behavior of their bands' energy positions relative to their bandgap energies.
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