Boosting photocatalytic hydrogen evolution enabled by SiO_(2)-supporting chiral covalent organic frameworks with parallel stacking sequence

Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.

Drainage evolution in intermontane basins at the Qinling-Daba Mountains

River capture is of great significance to landform evolution and hominine migration.In the Qinling-Daba Mountains,there is a viewpoint that Jialing River captured Hanjiang River,but this is still controversial.In this paper,we discuss the drainage evolution processes in intermountain basins at the Qinling-Daba Mountains based on a combination of detrital zircon UPb geochronology and geomorphic indexes.We suggest that the Hanjiang River gradually captured the Jialing River from east to west,accompanied by the evolution of the ancient Yangtze River.In terms of geomorphic evidences,wide valleys did not match with discharge,and a series of wind gaps developed in the Shiquan-Ankang basin.In addition,the valley shapes and width-toheight ratios(Vf)indicate two possible rapid incisions.The hypsometric integrals(HI)reflect that the landform gradually changes from the old stage to the youth stage from west to east.Theχvalues show that the drainage divide is moving to the side of the Yuehe River,and the Yuehe River is gradually shrinking.According to the sedimentary records,the zircon U-Pb age distributions indicate the provenance change.The high-altitude terraces show three age peaks(200–250,400–505,and 700–900 Ma),with the dominant Indosinian age peak(200–250 Ma),while the modern fluvial sediments only show a single peak of Jinning(700–900 Ma).These data show that there are two major river captures:(1)The ancient Hanjiang River cut through the regional compression ridge,and then captured the Hanzhong Basin river system(a part of the ancient Jialing river system)from east to west,and(2)The southern tributary captured the trunk with the uplift of the divide in the Shiquan-Ankang Basin,forming the modern drainage pattern in the upper Hanjiang River.The activities of the regional strike-slip fault,and the associated compression uplift played a key role in the river captures,the drainage evolution,and related landforms in the Shiquan-Ankang basin.In addition,it is shown that the evolution of the upper tributary basins lagged behind the response of the trunk channel to the tectonic activities and river captures.The interconnected wide valleys caused by river capture may have provided convenient geomorphological conditions for human migration into the Qinling-Daba Mountains along those river valleys.