Rational engineering of oxygen vacancy(VO) at atomic precision is the key to comprehensively understanding the oxygen chemistry of oxide materials for catalytic oxidations. Here, we demonstrate that VO can be spatiall...Rational engineering of oxygen vacancy(VO) at atomic precision is the key to comprehensively understanding the oxygen chemistry of oxide materials for catalytic oxidations. Here, we demonstrate that VO can be spatially confined on the surface through a sophisticated surface hydrogen bond(HB) network.The HB network is constructed between a hydroxyl-rich Bi OCl surface and polyprotic phosphoric acid,which remarkably decreases the formation energy of surface VO by selectively weakening the metal–oxygen bonds in a short range. Thus, surface-confined VO enables us to unambiguously distinguish the intrafacial and suprafacial oxygen species associated with NO oxidation in two classical catalytic systems.Unlike randomly distributed bulk VO that benefits the thermocatalytic NO oxidation and lattice O diffusion by the dominant intrafacial mechanism, surface VOis demonstrated to favor the photocatalytic NO oxidation through a suprafacial scheme by energetically activating surface O2, which should be attributed to the spatial confinement nature of surface VO.展开更多
基金the National Key Research and Development Program of China (2016YFA0203000)National Natural Science Funds for Distinguished Young Scholars (21425728)+2 种基金the National Natural Science Foundation of China (21872061)111 Project (B17019)Self-Determined Research Funds of CCNU from the Colleges’ Basic Research and Operation of MOE (CCNU16A02029)。
文摘Rational engineering of oxygen vacancy(VO) at atomic precision is the key to comprehensively understanding the oxygen chemistry of oxide materials for catalytic oxidations. Here, we demonstrate that VO can be spatially confined on the surface through a sophisticated surface hydrogen bond(HB) network.The HB network is constructed between a hydroxyl-rich Bi OCl surface and polyprotic phosphoric acid,which remarkably decreases the formation energy of surface VO by selectively weakening the metal–oxygen bonds in a short range. Thus, surface-confined VO enables us to unambiguously distinguish the intrafacial and suprafacial oxygen species associated with NO oxidation in two classical catalytic systems.Unlike randomly distributed bulk VO that benefits the thermocatalytic NO oxidation and lattice O diffusion by the dominant intrafacial mechanism, surface VOis demonstrated to favor the photocatalytic NO oxidation through a suprafacial scheme by energetically activating surface O2, which should be attributed to the spatial confinement nature of surface VO.
