Engineering Cu^(+)/CeZrO_(x) interfaces to promote CO_(2) hydrogenation to methanol

Cu-based catalysts are widely employed for CO_(2) hydrogenation to methanol,which is expected as a promising process to achieving carbon neutrality.However,most Cu-based catalysts still suffer from low methanol yield with a passable CO_(2) conversion and lack insight into its reaction mechanism for guiding the design of catalysts.In this work,Cu^(+)/CeZrO_(x) interfaces are engineered by employing a series of ceria-zirconia solid solution catalysts with various Ce/Zr ratios,forming a Cu^(+)-O_(v)-Ce^(3+)structure where Cu^(+)atoms are bonded to the oxygen vacancies(O_(v))of ceria.Compared to Cu/CeO_(2) and Cu/ZrO_(2),the optimized catalyst(i.e.,Cu_(0.3)Ce_(0.3)Zr_(0.7))exhibits a much higher mass-specific methanol formation rate(192g_(MeOH)/kg_(cat)/h)at 240℃and 3 MPa.Through a series of in-situ and ex-situ characterization,it is revealed that oxygen vacancies in solid solutions can effectively assist the activation of CO_(2) and tune the electronic state of copper to promote the formation of Cu^(+)/CeZrO_(x) interfaces,which stabilizes the key*CO intermediate,inhibits its desorption and facilitates its further hydrogenation to methanol via the reverse watergas-shift(RWGS)+CO-Hydro pathway.Therefore,the concentration of*CO or the apparent Cu^(+)/(Cu^(+)+Cu^(0))ratio could be employed as a quantitative descriptor of the methanol formation rate.This work is expected to give a deep insight into the mechanism of metal/support interfaces in CO_(2) hydrogenation to methanol,offering an effective strategy to develop new catalysts with high performance.

Is there a great unconformity between Xiamaling and Longshan formations in the North China Craton?

The existence of a 0.3 Ga"great unconformity"between the Mesoproterozoic"Undefined System"Xiamaling Formation and the"Neoproterozoic"Longshan Formation has long been controversial.In this study,stratigraphy,sedimentology,detrital zircon dating,lithium isotope,and major and trace elements were applied to systematically analyze their relationship.Results demonstrate that coarse to fine sandstone-mudstone normal cycles with different grades and thicknesses exist from the Xiamaling to the Longshan formations.Sedimentary succession formed from a restricted platform with lagoon-shallow marine shelf-tidal flat-beach and tidal shoal developing in ascending order.The pebbly sandstone at the bottom of the Long shan Formation does not have the properties of basal conglomerate with tectonic significance.The youngest detrital zircon is older than 1.6 Ga for the Long shan Formation and overlying Jing'eryu Formation sandstones.In addition,no(zircon)provenance has been found from the large igneous province of 1.32-1.2 Ga in Xiamaling Formation.Theδ^(7)Li isotope values exhibit a gradually increasing trend.The Li content and CIA(Chemical index of alteration)gradually decreases from the top of the Xiamaling Formation to the lower part of the Long shan Formation.Simultaneously,as K_(2)O/Al_(2)O_(3)and FeO/Fe_(2)O_(3)decreases,Na_(2)O/Al_(2)O_(3)increases,and Li/Al,V/Cr,and V/(V+Ni)fluctuates slightly.At the boundary,the Ce/Ce^(*)and Eu/Eu^(*)show positive and negative anomalies,respectively.Further,the Rb/Sr and Al/Si values decrease,and U/Th values increase.This indicates that the geochemistry of the weathering crust at the interface of the Xiamaling Formation-Long shan Formation is not characteristic.However,it indicates a weakening of continental weathering intensity from the bottom to the top of the interface.These results do not support the existence of a large unconformity between the Xiamaling and the Longshan formations.Therefore,it is suggested that the Long shan Formation-Jing'eryu Formation should be moved to the lower level in the stratigraphic chart,where it should form part of the Mesoproterozoic"Undefined System"along with the Xiamaling Formation.On this basis,the paleogeography of the Xiamaling Formation-Longshan Formation-Jing'eryu Formation sedimentary period in the Yanliao area of North China has been reclassified.