Core@shell catalysts based on nickel phyllosilicates for dry reforming of methane: Effects of aging under hydrolysis conditions

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General Pub Date : 2025-09-23 DOI:10.1016/j.apcata.2025.120593

Breno C. da Silva , Igor R. Neves , Pedro H.C. Bastos , Vitor S. Queiroz , Noemi R.C. Huaman , Maria L.A. da Silva , Roger Frety , Soraia T. Brandao

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引用次数: 0

Abstract

A new method for synthesis of catalysts with core@shell architecture has been developed for syngas production via dry reforming of methane (DRM). This route is based on the confinement of Stöber particles (silica nanospheres) by nickel phyllosilicates and a layer-analogous decoration made of SiO₂ (shell). Dry reforming catalysts based on non-noble metals suffer from deactivation via sintering and coke formation. Core@shell structures offer a strategy to enhance stability and control metal dispersion. In this work, the Stöber particles were obtained and then nickel phyllosilicate was synthetized over them (NiPS); silica was deposited on the resulting material producing a decorated material (S0@NiPS) and the effect of its aging under hydrolysis conditions for 12, 24, 36 and 48 h was evaluated (S12, S24, S36 and S48@NiPS). It was possible to demonstrate the efficiency of the proposed structures, with reagent conversion above 90 %, good yield to syngas and no signs of deactivation in the catalytic test at 700°C (coking condition), for the S24@NiPS sample (reducible nickel content 8 % w/w). The superior activity of S24@NiPS is attributed to optimal Ni dispersion and shell structure, balancing accessibility and confinement. The order of activity obtained was: S24@NiPS > S12@NiPS > NiPS > S36@NiPS > S48@NiPS > S0@NiPS. The materials were characterized by XRD, TPR-H2, TPO-O2, TEM, EDS and TPSR-DRM. The modification of the hydrolysis time changed the properties of the catalysts: the shortest and longest times generated the less active catalysts. These findings offer a route to a coke-resistant catalysts for CO₂ valorization and methane upgrading.

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Core@shell层状硅酸盐镍基甲烷干重整催化剂：水解条件下老化的影响

开发了一种新型结构为core@shell的甲烷干重整合成气催化剂的合成方法。这种方法是基于层状硅酸盐镍对Stöber粒子（二氧化硅纳米球）的约束和由二氧化硅（外壳）制成的层状类似装饰。基于非贵金属的干重整催化剂会因烧结和结焦而失活。Core@shell结构提供了一种增强稳定性和控制金属分散的策略。本文制备了Stöber颗粒，并在其上合成了层状硅酸镍（NiPS）；将二氧化硅沉积在得到的材料上，得到装饰材料（S0@NiPS），并评估其在12、24、36和48 h水解条件下的老化效果（S12、S24、S36和S48@NiPS）。对于S24@NiPS样品（可还原镍含量为8 % w/w），在700°C（焦化条件）的催化测试中，可以证明所提出结构的效率，试剂转化率高于90 %，合成气收率高，没有失活迹象。S24@NiPS的优异活性归因于最佳的Ni分散和壳结构，平衡了可及性和约束。活动获得的顺序是:S24@NiPS祝辞 S12@NiPS祝辞 捏祝辞 S36@NiPS祝辞 S48@NiPS祝辞 S0@NiPS。采用XRD、TPR-H2、TPO-O2、TEM、EDS和TPSR-DRM对材料进行了表征。水解时间的改变改变了催化剂的性能，最短和最长的水解时间产生的催化剂活性较低。这些发现为CO 2增值和甲烷升级的抗焦催化剂提供了一条途径。

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来源期刊

Applied Catalysis A: General 化学-环境科学

CiteScore

9.00

自引率

5.50%

发文量

415

审稿时长

24 days

期刊介绍： Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.