| During the past three decades,metal chalcogenide supertetrahedral clusters(0D)have become the hot research topics due to their nanoscale cluster size,multifarious compositions,well-defined atom locations and semiconducting behaviors.Such 0D supertetrahedral clusters can be assembled into cluster-based crystalline 2D layers and 3D open frameworks through sharing the corner sulfur atoms.These crystalline materials not only retain the inherent properties of 0D chalcogenide supertetrahedral clusters,but also provides new characteristics from 2D layers and 3D open frameworks,which effectively integrate the porosity with semiconducting properties.However,it becomes very difficult to construct new materials now because of the limited cluster kinds and rigid inter-cluster connection modes.It is challenging but meaningful to build new cluster-based crystalline materials through modifying the reaction condition.Herein,a new 0D chalcogenide cluster was successfully prepared and dispersed,and the related photocatalytic performance were further studied.Besides,a group of new cluster-based 2D layers and 3D open-frameworks were also constructed through intentionally introducing tetravalent-metal ions in reaction media.Furthermore,the photocatalytic and electrocatalytic properties of above materials were explored.The main contents of this thesis are as follows:(1)A 0D supertetrahedral chalcogenide T4 cluster was achieved,and the photocatalytic performance for the composites of T4@g-C3N4 was also studied.This work emphasized the significant roles of cluster-dispersion and energy band modulation on the influence of photocatalytic performance.(2)Two new layered chalcogenide frameworks with interrupted sites were synthesized,and the significant roles of tetravalent metal ions in building layered frameworks were also advanced.(3)A gsi topology structure with a large inter-cluster bridging angle was built,which represents a new topology family member of metal chalcogenides. |
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