摘要：Selective hydrodeoxygenation of lignin derivatives into aromatic compounds is a promising route for the upgrading of lignin *** carbide catalysts have exhibited excellent selectivity in hydrodeoxygenation reactions,while their structure-activity relationship is still in ***,a liquid-phase atomic layer deposition method was employed to synthesize W_(2)C/SiO_(2) catalysts with uniform and size-controllable W_(2)C *** gas-phase hydrodeoxygenation of lignin-derived m-cresol at 350℃,these W_(2)C/SiO_(2) catalysts showed superior toluene selectivities(>95%)regardless of the W_(2)C particle *** optimal W_(2)C particle size of~7 nm was obtained for achieving the highest W_(2)C-based hydrodeoxygenation *** contrast,the turnover rate per surface W site increased almost monotonously as the W_(2)C particle size increased within 0.7-15 nm,attributable to high-index planes appeared on the larger W_(2)C *** effects of m-cresol and H_(2),taken together with temperature-programmed desorption of probe molecules and theoretical treatments,further indicate that the W_(2)C surface is nearly saturated by adsorbed m-cresol or its derivates under the reaction condition and the H-addition of the C7H7*intermediate to form toluene,instead of the initial C-O cleavage in m-cresol,acts as the rate-determining step.A side-by-side comparison between W_(2)C(102)and W_(2)C(001)catalyst surfaces in theoretical simulations of m-cresol hydrodeoxygenation verifies that high-index planes can stabilize kinetically-relevant transition states more effectively than the low-index ones,as a result of more available less-coordinated active sites on the *** above findings bring new mechanistic insights into the site requirements of supported W_(2)C nanocatalysts,distinct from those metal-catalyzed hydrodeoxygenation of oxygenates.

摘要：Layered double hydroxides(LDHs),a class of two-dimensional(2D)brucite-like layers,have been effectively applied in diverse ***,the current synthesis methods restrict the in situ scaling-up and tunable production of LDH-based *** by the growing characteristic of“Bryophyllum pinnatum”,a sacrificial co-sputtered Zn-Al transition layer was introduced for the first time to in situ grow a scalable-manufactured and thickness-controllable LDH film on arbitrary substrate materials with flexible shapes through“partial dissolution”and“solution infiltration”*** LDH films could be tailored by the creative regulation of the component,structure and surface state of the transition *** showed that the as-prepared LDH film had strong mechanical robustness under harsh abrasion conditions due to its large thickness and multi-level ***,a series of galvanic couple model experiments based on Zn/Al single-metal transition layers were designed to solve the real-time monitoring issue in the complex hydrothermal *** work not only develops a new strategy to design and grow in situ LDH films with multifaceted features,but also reveals sophisticated LDH formation ***,the findings of this study may broaden the practical application of LDH-based materials toward advanced and smart devices.