The valence state analysis of MnO_x/Ti₄O₇ samples at different calcination temperatures obtained from XPS.

Sample name	Orbit	Binding energy/eV	Area	Ratio of Mn3+/Mn2+
MnOx/Ti4O7-RT	Mn3+-2p3/2	641.6	10 002	0.699
	Mn2+-2p3/2	641.1	14 306
	Mn3+-2p1/2	653.3	5001
	Mn2+-2p1/2	653.0	7153
MnOx/Ti4O7-200	Mn3+-2p3/2	641.6	6842	0.530
	Mn2+-2p3/2	641.1	12 901
	Mn3+-2p1/2	653.3	3421
	Mn2+-2p1/2	653.0	6451
MnOx/Ti4O7-300	Mn3+-2p3/2	641.6	12 850	1.552
	Mn2+-2p3/2	641.1	8280
	Mn3+-2p1/2	653.3	6425
	Mn2+-2p1/2	653.0	4140
MnOx/Ti4O7-400	Mn3+-2p3/2	641.6	6939	0.567
	Mn2+-2p3/2	641.1	12 231
	Mn3+-2p1/2	653.3	3469
	Mn2+-2p1/2	653.0	6115