Catalytic　oxidation　of　CO,　benzene,　and　toluene　was　studied　over　the　octahedral　layered　birnessites　(OL-1,　OL-2,　OL-3,　and　OL-4)　derived　from　different　routes.　Physicochemical　properties　of　the　samples　were　characterized　by　a　number　of　different　analytical　techniques.　It　is　found　that　all　of　the　samples　have　birnessite-type　octahedral　layered　structure　and　an　interlayer　spacing　of　ca.　0.72　nm.　Surface　areas　and　pore　volumes　of　the　OL-3　and　OL-4　samples　were　much　higher　than　those　of　the　OL-1　and　OL-2　samples.　There　was　co-presence　of　Mn3+,　Mn4+　and/or　Mn2+　on　the　surface　of　these　samples.　Based　on　the　manganese　ion　contents,　the　average　oxidation　states　of　surface　Mn　species　in　the　birnessite　samples　were　in　the　range　of　3.2-3.5,　which　was　lower　than　those　(3.5-3.9)　obtained　from　the　H2-TPR　studies.　The　amounts　of　oxygen　vacancies　and　lattice　oxygen　mobility　of　the　OL-1　and　OL-4　samples　were　higher　than　those　of　the　OL-2　and　OL-3　samples.　Either　in　CO　oxidation　or　in　benzene　or　toluene　oxidation,　the　catalytic　activity　decreased　in　the　order　of　OL-1　＞　OL-4　OL-3　＞　OL-2,　with　the　OL-1　sample　showing　the　best　performance　(T-50%　=　115　and　T-100%　=　150　degrees　C　for　CO　oxidation　at　15,000　mL/(g　h),　T50%　=200　degrees　C　and　T-95%　=　240　degrees　C　for　benzene　oxidation,　and　T-50%　=190　degrees　C　and　T-95%　=230　degrees　C　for　toluene　oxidation　at　40,000　mL/(gh)).　We　conclude　that　catalytic　performance　of　the　octahedral　layered　birnessite　samples　was　associated　with　the　Mn　oxide　nature,　surface　lattice　oxygen　mobility,　and　reducibility.　(C)　2014　Elsevier　B.V.　All　rights　reserved.