Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also...Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also strongly on the chemical nature of the iron oxide.In this study,Au NPs supported on iron oxide nanorods with different surface properties throughβ-FeOOH annealing,at varying temperatures,were synthesized,and applied in the CO oxidation.Detailed characterizations of the interactions between Au NPs and iron oxides were obtained by X-ray diffraction,transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy.The results indicate that the surface hydroxyl group on the Au/FeOOH catalyst,before calcination(Au/FeOOH-fresh),could facilitate the oxygen adsorption and dissociation on positively charged Au,thereby contributing to the low-temperature CO oxidation reactivity.After calcination at 200℃,under air exposure,the chemical state of the supported Au NP on varied iron oxides partly changed from metal cation to Au0,along with the disappearance of the surface OH species.Au/FeOOH with the highest Au0 content exhibits the highest activity in CO oxidation,among the as-synthesized catalysts.Furthermore,good durability in CO oxidation was achieved over the Au/FeOOH catalyst for 12 h without observable deactivation.In addition,the advanced identical-location TEM method was applied to the gas phase reaction to probe the structure evolution of the Au/iron oxide series of the catalysts and support structure.A Au NP size-dependent Ostwald ripening process mediated by the transport of Au(CO)x mobile species under certain reaction conditions is proposed,which offers a new insight into the validity of the structure-performance relationship.展开更多
Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand t...Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand to tune the selectivity of propane oxidative dehydrogenation. Beneficial from the weakened affinity of propene, NiO modified with polymeric phosphate shows a selectivity 2–3 times higher than NiO towards the production of propene. The success of this regulation verifies the feasibility of ligand modification in high-temperature gas-phase reactions and shines a light on its applications in other important industrial reactions.展开更多
Nanomaterials have attracted considerable interest owing to their unique physicochemical properties.The wide application of nanomaterials has raised many concerns about their potential risks to human health and the en...Nanomaterials have attracted considerable interest owing to their unique physicochemical properties.The wide application of nanomaterials has raised many concerns about their potential risks to human health and the environment.Metal oxide nanopartides（MONPs）,one of the main members of nanomaterials,have been applied in various fields,such as food,medicine,cosmetics,and sensors.This review highlights the bio-toxic effects of widely applied MONPs and their underlying mechanisms.Two main underlying toxicity mechanisms,reactive oxygen species（ROS）-and non-ROS-mediated toxidties,of MONPs have been widely accepted.ROS activates oxidative stress,which leads to lipid peroxidation and cell membrane damage.In addition,ROS can trigger the apoptotic pathway by activating caspase-9 and-3.Non-ROS-mediated toxicity mechanism includes the effect of released ions,excessive accumulation of NPs on the cell surface,and combination of NPs with specific death receptors.Furthermore,the combined toxicity evaluation of some MONPs is also discussed.Toxicity may dramatically change when nanomaterials are used in a combined system because the characteristics of NPs that play a key role in their toxicity such as size,surface properties,and chemical nature in the complex system are different from the pristine NPs.展开更多
基金supported by the National Natural Science Foundation of China(21773269,21761132025,91545119,21703262)the Youth Innovation Promotion Association CAS(2015152)+1 种基金the Joint Foundation of Liaoning Province Natural Science FoundationShenyang National Laboratory for Materials Science(20180510047)~~
文摘Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also strongly on the chemical nature of the iron oxide.In this study,Au NPs supported on iron oxide nanorods with different surface properties throughβ-FeOOH annealing,at varying temperatures,were synthesized,and applied in the CO oxidation.Detailed characterizations of the interactions between Au NPs and iron oxides were obtained by X-ray diffraction,transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy.The results indicate that the surface hydroxyl group on the Au/FeOOH catalyst,before calcination(Au/FeOOH-fresh),could facilitate the oxygen adsorption and dissociation on positively charged Au,thereby contributing to the low-temperature CO oxidation reactivity.After calcination at 200℃,under air exposure,the chemical state of the supported Au NP on varied iron oxides partly changed from metal cation to Au0,along with the disappearance of the surface OH species.Au/FeOOH with the highest Au0 content exhibits the highest activity in CO oxidation,among the as-synthesized catalysts.Furthermore,good durability in CO oxidation was achieved over the Au/FeOOH catalyst for 12 h without observable deactivation.In addition,the advanced identical-location TEM method was applied to the gas phase reaction to probe the structure evolution of the Au/iron oxide series of the catalysts and support structure.A Au NP size-dependent Ostwald ripening process mediated by the transport of Au(CO)x mobile species under certain reaction conditions is proposed,which offers a new insight into the validity of the structure-performance relationship.
基金was supported by the National Natural Science Foundation of China(91545113,21703050)the China Postdoctoral Science Foundation(2017M610363,2018T110584)+2 种基金Shell Global Solutions International B.V.(PT71423,PT74557)the Fok Ying Tong Education Foundation(131015)the Science&Technology Program of Ningbo(2017C50014)~~
文摘Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand to tune the selectivity of propane oxidative dehydrogenation. Beneficial from the weakened affinity of propene, NiO modified with polymeric phosphate shows a selectivity 2–3 times higher than NiO towards the production of propene. The success of this regulation verifies the feasibility of ligand modification in high-temperature gas-phase reactions and shines a light on its applications in other important industrial reactions.
基金supported by the National Natural Science Foundation of China(21371115,11025526,40830744, 41073073,and 21101104)the National Basic Research Program of China(2011CB933402)+1 种基金the Innovation Program of Shanghai Municipal Education Commission(14YZ025)the Program for Innovative Research Team in University(IRT13078)
文摘Nanomaterials have attracted considerable interest owing to their unique physicochemical properties.The wide application of nanomaterials has raised many concerns about their potential risks to human health and the environment.Metal oxide nanopartides（MONPs）,one of the main members of nanomaterials,have been applied in various fields,such as food,medicine,cosmetics,and sensors.This review highlights the bio-toxic effects of widely applied MONPs and their underlying mechanisms.Two main underlying toxicity mechanisms,reactive oxygen species（ROS）-and non-ROS-mediated toxidties,of MONPs have been widely accepted.ROS activates oxidative stress,which leads to lipid peroxidation and cell membrane damage.In addition,ROS can trigger the apoptotic pathway by activating caspase-9 and-3.Non-ROS-mediated toxicity mechanism includes the effect of released ions,excessive accumulation of NPs on the cell surface,and combination of NPs with specific death receptors.Furthermore,the combined toxicity evaluation of some MONPs is also discussed.Toxicity may dramatically change when nanomaterials are used in a combined system because the characteristics of NPs that play a key role in their toxicity such as size,surface properties,and chemical nature in the complex system are different from the pristine NPs.
