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Effects of specific nitrogen functionality and oxidative functionalization of the surfaces of nitrogen-doped carbon nanotubes (NCNTs) on the interaction between Pt nanoparticles (NPs) and NCNTs have been systematically investigated. Their catalytic consequences were studied using aerobic oxidation of glycerol and electro-oxidation of CO as probing reactions. By transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and X-ray diffraction (XRD), it was revealed that nitrogen dopant obviously enhanced the dispersion of Pt NPs. Strong interaction between Pt and NCNTs was observed. Graphitic nitrogen preferentially interacted with Pt NPs, evidenced by strong electron transfer from graphitic nitrogen as electron donor to metallic Pt NPs. The oxygen-containing groups introduced by H 2 O 2 oxidation of NCNTs may reduce the donor–acceptor interaction due to the electronegativity of oxygen. By changing the nitrogen amount of NCNTs and introducing oxygen groups, the electron enrichment of Pt NPs can be tuned. Superior catalytic activity was achieved over Pt/NCNTs in the oxidation of glycerol and electro-oxidation of CO, compared with conventional carbon nanotubes as support. Moreover, for both aerobic oxidation of glycerol and electro-oxidation of CO, it was observed that the intrinsic activity depended strongly on the electron enrichment of Pt NPs, ascribed to Pt4 f 7/2 (0) binding energy from XPS, suggesting a promising approach to improving catalytic activity by maximizing the interaction between Pt NPs and graphitic nitrogen sites. [ABSTRACT FROM AUTHOR]

Abstract: Adsorption of acidified multiwalled carbon nanotubes (MWCNTs) to heavy metal using Pb(II) as a model was investigated and characterized by many techniques. The main adsorption mechanism of acidified MWCNTs to Pb(II) is proposed on the basis of adequate analysis. The results show that the oxygenous functional groups can be formed on MWCNTs after MWCNTs were treated by concentrated nitric acid. The oxygenous functional groups play an important role in Pb(II) adsorption to form chemical complex adsorption, which accounts for 75.3% of all the Pb(II) adsorption capacity. The Pb(II) in the form of PbO, Pb(OH)2, and PbCO3 adsorbed on the surface of the acidified MWCNTs is only 3.4% of the total Pb(II) adsorption capacity. The Pb(II) species adsorbed on acidified MWCNTs mainly aggregate on the ends and at the defects sites on the acidified MWCNTs. [Copyright &y& Elsevier]

The influence of catalyst synthesis strategy, including ethylene glycol (EG) reduction, sodium borohydride reduction and impregnation-H 2 -reduction, on the metal-support-interaction of Pt on nitrogen-doped carbon nanotubes (Pt/NCNTs) was systematically investigated and summarized. The catalytic performances were explored in the electro-oxidation reactions of glycerol, formic acid and CO, and the hydrolysis of ammonia borane (AB). Through X-ray photoelectron spectroscopy (XPS), density functional theory calculations and CO stripping technique, it was revealed that the synthesis methods drastically affected the electronic property of Pt nanoparticles (NPs). Pt NPs preferentially interacted with graphitic nitrogen in EG reduction method due to the electron donating property of graphitic nitrogen, while preferentially interacted with pyridinic nitrogen and defects in the impregnation-H 2 -reduction method due to the vacancies containing N P favoring the charged metal ion adsorption. The catalytic activity strongly depended on the electronic property of Pt NPs, which can be ascribed by the binding energy of Pt4f 7/2 (0) from XPS. The higher catalytic activity was obtained over electron-enriched Pt NPs for the electro-oxidation reactions. On the other hand, electron-deficient Pt NPs had better intrinsic activity in AB hydrolysis. The results herein suggested that appropriate synthesis method should be rationally applied to maximize the activities of Pt for targeting reactions benefited from electron-enriched or electron-deficient metal NPs. [ABSTRACT FROM AUTHOR]

The group 15 metals, bismuth and antimony, play important roles in promoting noble-metal-catalyzed oxidation reactions toward high value-added chemicals. Herein, we report that the selective oxidation of glycerol to 1,3-dihydroxyacetone (DHA) catalyzed by Pt supported on N-doped carbon nanotubes (Pt/NCNT) can be significantly promoted in the presence of Bi or Sb in reaction solution. This catalyst system showed not only comparable even better performance to the Pt/NCNT with pre-loaded Bi, but also the greatly simplified catalyst preparation. It was found that the Bi-promoted Pt/NCNT underwent dynamic surface reconstruction through leaching and adsorption of Bi adatoms, due to the formation of glyceric acid. By characterizing the adsorption of Bi on Pt catalyst with high-resolution transmission electron microscopy, CO-stripping, horizontal attenuated total reflection infrared spectroscopy and X-ray photoelectron spectroscopy, it has been ascertained that Bi preferentially deposits on the step sites of Pt, and then blocks the terrace sites to promote the Pt catalyst mainly through a geometrical effect, which facilitates the activation and transformation of the secondary hydroxyl group of glycerol through the chelation between substrate and Pt–Bi sites. [ABSTRACT FROM AUTHOR]