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壳聚糖包覆的贵金属掺杂 CeO 纳米材料:合成及其增强的催化活性。

Chitosan capped noble metal doped CeO nanomaterial: Synthesis, and their enhanced catalytic activities.

机构信息

Department of Chemistry, Faculty of Science, King Abdulaziz University, P. O. Box 80203, Jeddah 21589, Saudi Arabia.

出版信息

Int J Biol Macromol. 2021 Jan 1;166:1258-1271. doi: 10.1016/j.ijbiomac.2020.11.008. Epub 2020 Nov 4.

Abstract

Chitosan (Ch) capped Ch-CeO, Ch-CeO/Ag, Ch-CeO/Pd and Ch-CeO/Ag/Pd nanomaterials were fabricated using seedless and metal displacement plating method. The Ce ions first formed complex with Ch through amino and hydroxyl groups and then reduced in presence of NaOH and molecular oxygen at higher temperature. Ch-Ag and Ch-Pd complexes adsorbed on the surface of Ch-CeO and reduced under potential deposition. Ninhydrin reaction test was conducted to confirm the presence of chitosan on the surface of NMs. The catalytic efficiency was increases markedly with incorporating noble metal into Ch-CeO NMs. Ch-CeO/Ag/Pd exhibits higher catalytic performance towards hydrogen generation due to the narrow band gap (2.65 eV) and smaller work function of CeO (ϕ = 2.8 eV) than that of Ag(ϕ =4.6 eV) and Pd (ϕ = 5.2 eV). Hydrogen generation rates increases with temperature and activation energies were found to be 63.2, 60.3, 56.2 and 53.0 kJ/mol for Ch-CeO, Ch-CeO/Ag, Ch-CeO/Pd, and Ch-CeO/Ag/Pd, respectively. CeO/Ag/Pd shows better catalytic efficiency due to the strong interaction between Ag/Pd metal and active support CeO. The photocatalytic rates drastically inhibited with scavengers, demonstrate that the reactive radical oxygen species (HO and O), holes (h) and electrons (e) played major role in the NaBH hydrolysis.

摘要

壳聚糖(Ch)封端的 Ch-CeO、Ch-CeO/Ag、Ch-CeO/Pd 和 Ch-CeO/Ag/Pd 纳米材料是通过无种子和金属置换镀方法制备的。Ce 离子首先通过氨基和羟基与 Ch 形成配合物,然后在较高温度下在 NaOH 和分子氧存在下还原。Ch-Ag 和 Ch-Pd 配合物吸附在 Ch-CeO 的表面上,并在电势沉积下还原。茚三酮反应试验证实了纳米材料表面存在壳聚糖。将贵金属掺入 Ch-CeO 纳米材料中会显著提高催化效率。由于 CeO 的带隙(2.65 eV)和功函数(ϕ=2.8 eV)小于 Ag(ϕ=4.6 eV)和 Pd(ϕ=5.2 eV),因此 Ch-CeO/Ag/Pd 对氢气生成表现出更高的催化性能。氢气生成速率随温度升高而增加,Ch-CeO、Ch-CeO/Ag、Ch-CeO/Pd 和 Ch-CeO/Ag/Pd 的活化能分别为 63.2、60.3、56.2 和 53.0 kJ/mol。CeO/Ag/Pd 具有更好的催化效率,因为 Ag/Pd 金属与活性载体 CeO 之间存在强烈相互作用。光催化速率随清除剂急剧抑制,表明活性自由基氧物种(HO 和 O)、空穴(h)和电子(e)在 NaBH 水解中起主要作用。

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