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含镍和钴的沸石材料:柠檬醛选择性加氢的合成及催化潜力

Zeolite materials with Ni and Co: synthesis and catalytic potential in the selective hydrogenation of citral.

作者信息

Rodríguez-Iznaga Inocente, Costa Marrero Yailen, Farias Piñeira Tania, Fontaine Céline, Paget Lexane, Concepción Rosabal Beatriz, Penton Madrigal Arbelio, Petranovskii Vitalii, Lafaye Gwendoline

机构信息

Instituto de Ciencia y Tecnología de Materiales (IMRE), Universidad de La Habana, Zapata y G, 10400, La Habana, Cuba.

Universidad de las Ciencias Informáticas, Carretera a San Antonio km 21/2, 19370, La Habana, Cuba.

出版信息

Beilstein J Nanotechnol. 2025 Apr 14;16:520-529. doi: 10.3762/bjnano.16.40. eCollection 2025.

Abstract

Zeolitic materials incorporating mono- and bimetallic systems of nickel and cobalt were obtained from natural zeolite modified with Ni and Co chloride solutions through traditional ion exchange (IE) and impregnation (Imp) processes. Special attention was given to analyzing the cationic and anionic composition of the resulting materials. The catalytic potential was evaluated in the selective hydrogenation of citral, focused on the formation of unsaturated alcohols. The IE process replaced mainly Ca and Na with Ni and Co cations in the zeolite phases (clinoptilolite and mordenite mix), while Imp resulted in higher metal content (2.0-2.7%) but retained significant amounts of chloride (1.9-3.8%), as confirmed by XRD and temperature-programmed reduction. The materials prepared by IE had negligible chloride content (0.02-0.07%), and their specific surface areas (138-146 m/g) were greater than those of the materials obtained by Imp (54-67 m/g). The bimetallic systems exhibited enhanced reducibility of the Co and Ni isolated cations, attributed to synergistic interactions that weakened the cation-framework binding. Catalytic activity tests showed that nickel species were primarily responsible for citronellal formation. Among all materials, the bimetallic CoNi catalyst, prepared by IE, was the only one to produce unsaturated alcohols, suggesting that synergistic Ni-Co interactions played a role in their formation.

摘要

通过传统的离子交换(IE)和浸渍(Imp)工艺,用氯化镍和氯化钴溶液对天然沸石进行改性,得到了包含镍和钴的单金属及双金属体系的沸石材料。特别关注了所得材料的阳离子和阴离子组成。在柠檬醛的选择性氢化反应中评估了催化潜力,重点是不饱和醇的形成。离子交换过程主要用镍和钴阳离子取代了沸石相(斜发沸石和丝光沸石混合物)中的钙和钠阳离子,而浸渍法导致更高的金属含量(2.0 - 2.7%),但保留了大量的氯(1.9 - 3.8%),X射线衍射(XRD)和程序升温还原证实了这一点。通过离子交换制备的材料氯含量可忽略不计(0.02 - 0.07%),其比表面积(138 - 146 m²/g)大于通过浸渍法获得的材料(54 - 67 m²/g)。双金属体系表现出钴和镍孤立阳离子的还原性增强,这归因于协同相互作用削弱了阳离子与骨架的结合。催化活性测试表明,镍物种主要负责香茅醛的形成。在所有材料中,通过离子交换制备的双金属钴镍催化剂是唯一能产生不饱和醇的催化剂,这表明镍 - 钴协同相互作用在其形成过程中发挥了作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/65af/12018909/a6b56c20a726/Beilstein_J_Nanotechnol-16-520-g002.jpg

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