Catalytic performance of detonation nanodiamonds in n-hexane conversion: Structure-activity relationship and surface chemistry effects

IF 4.3 3区材料科学 Q2 MATERIALS SCIENCE, COATINGS & FILMS

Diamond and Related Materials Pub Date : 2025-05-07 DOI:10.1016/j.diamond.2025.112423

Anastasia S. Chizhikova, Anna N. Matveyeva, Maria O. Enikeeva, Nadejda A. Belskaya, Ekaterina Yu. Stovpiaga, Andrey D. Trofimuk, Aleksander E. Aleksenskii, Vadim I. Popkov, Alexander Ya. Vul’

{"title":"Catalytic performance of detonation nanodiamonds in n-hexane conversion: Structure-activity relationship and surface chemistry effects","authors":"Anastasia S. Chizhikova, Anna N. Matveyeva, Maria O. Enikeeva, Nadejda A. Belskaya, Ekaterina Yu. Stovpiaga, Andrey D. Trofimuk, Aleksander E. Aleksenskii, Vadim I. Popkov, Alexander Ya. Vul’","doi":"10.1016/j.diamond.2025.112423","DOIUrl":null,"url":null,"abstract":"<div><div>Detonation nanodiamonds (DND) have emerged as promising metal-free catalysts for hydrocarbon processing due to their high surface area, structural stability, and chemically tunable surfaces. In this study, four types of DND – commercial (DND_in), purified (DND_pur), deaggregated (DND_deag), and residual DND fraction after the deaggregation process (DND_resid) – were comprehensively characterized and tested in the catalytic conversion of n-hexane to elucidate structure–activity relationships and the effects of surface chemistry. X-ray diffraction and Raman spectroscopy confirmed a nanocrystalline diamond core with crystallite sizes from 4.2 to 5.6 nm. BET surface areas ranged from 248 to 335 m<sup>2</sup>/g, and FTIR and elemental analysis revealed a substantial decrease in oxygen-containing functional groups after purification and deaggregation (oxygen content reduced from 10.1 to 3.4 at.%), accompanied by a reduction in sp<sup>2</sup>‑carbon. Nitrogen adsorption indicated mesoporosity with pore sizes of 7–20 nm, with DND_deag exhibiting the most compact texture and highest surface accessibility. Catalytic tests at 505 °C demonstrated high selectivity (>85 mol%) towards dehydrogenation and dehydrocyclization products for all samples. DND_deag showed the highest n-hexane conversion (18.3 %), followed by DND_pur (16.2 %) and DND_in (13.5 %). DND_in achieved the highest benzene selectivity (41 mol%) due to residual metal oxides, while DND_deag and DND_pur favored C2–C6 alkene formation (up to 40 mol%). These results demonstrate that increased surface area, lower sp<sup>2</sup>‑carbon content, and reduced oxygen functionalities strongly enhance catalytic performance and shift product distribution towards desired alkenes. Post-reaction analysis confirmed structural integrity and suggested that spent samples can be regenerated via mild oxidative treatment. This study highlights the potential of DND as efficient, reusable, and metal-free catalysts for sustainable hydrocarbon transformations.</div></div>","PeriodicalId":11266,"journal":{"name":"Diamond and Related Materials","volume":"156 ","pages":"Article 112423"},"PeriodicalIF":4.3000,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Diamond and Related Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0925963525004807","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, COATINGS & FILMS","Score":null,"Total":0}

引用次数: 0

Abstract

Detonation nanodiamonds (DND) have emerged as promising metal-free catalysts for hydrocarbon processing due to their high surface area, structural stability, and chemically tunable surfaces. In this study, four types of DND – commercial (DND_in), purified (DND_pur), deaggregated (DND_deag), and residual DND fraction after the deaggregation process (DND_resid) – were comprehensively characterized and tested in the catalytic conversion of n-hexane to elucidate structure–activity relationships and the effects of surface chemistry. X-ray diffraction and Raman spectroscopy confirmed a nanocrystalline diamond core with crystallite sizes from 4.2 to 5.6 nm. BET surface areas ranged from 248 to 335 m²/g, and FTIR and elemental analysis revealed a substantial decrease in oxygen-containing functional groups after purification and deaggregation (oxygen content reduced from 10.1 to 3.4 at.%), accompanied by a reduction in sp²‑carbon. Nitrogen adsorption indicated mesoporosity with pore sizes of 7–20 nm, with DND_deag exhibiting the most compact texture and highest surface accessibility. Catalytic tests at 505 °C demonstrated high selectivity (>85 mol%) towards dehydrogenation and dehydrocyclization products for all samples. DND_deag showed the highest n-hexane conversion (18.3 %), followed by DND_pur (16.2 %) and DND_in (13.5 %). DND_in achieved the highest benzene selectivity (41 mol%) due to residual metal oxides, while DND_deag and DND_pur favored C2–C6 alkene formation (up to 40 mol%). These results demonstrate that increased surface area, lower sp²‑carbon content, and reduced oxygen functionalities strongly enhance catalytic performance and shift product distribution towards desired alkenes. Post-reaction analysis confirmed structural integrity and suggested that spent samples can be regenerated via mild oxidative treatment. This study highlights the potential of DND as efficient, reusable, and metal-free catalysts for sustainable hydrocarbon transformations.

Abstract Image

查看原文本刊更多论文

爆轰纳米金刚石在正己烷转化中的催化性能：构效关系及表面化学效应

爆轰纳米金刚石（DND）由于其高表面积、结构稳定性和表面化学可调等优点，已成为一种很有前途的无金属碳氢化合物催化剂。在本研究中，对四种类型的DND -商业（DND_in）、纯化（DND_pur）、解聚（DND_deag）和解聚后的残余DND组分（DND_resid）进行了全面的表征和测试，以阐明其在正己烷催化转化中的构效关系和表面化学的影响。x射线衍射和拉曼光谱证实了一个纳米晶金刚石核，晶体尺寸在4.2 ~ 5.6 nm之间。BET的表面积从248到335 m2/g不等，FTIR和元素分析显示，经过纯化和解聚后，含氧官能团大幅减少（氧含量从10.1降至3.4 at.%），同时伴有sp2 -碳的减少。氮吸附表现为介孔结构，孔径为7 ~ 20 nm， DND_deag结构最致密，表面可达性最高。505°C的催化实验表明，所有样品的脱氢和脱氢环化产物具有高选择性（>85 mol%）。正己烷转化率最高的是DND_deag(18.3%)，其次是DND_pur（16.2%）和DND_in（13.5%）。DND_in对苯的选择性最高（41 mol%），而dnd_deg和DND_pur对C2-C6烯烃的选择性最高（40 mol%）。这些结果表明，增加的表面积、降低的sp2碳含量和降低的氧官能团强烈地增强了催化性能，并将产物分布转向所需的烯烃。反应后分析证实了结构的完整性，并表明废样品可以通过轻度氧化处理再生。这项研究强调了DND作为高效、可重复使用、无金属催化剂的潜力，可用于可持续的碳氢化合物转化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Diamond and Related Materials 工程技术-材料科学：综合

CiteScore

6.00

自引率

14.60%

发文量

702

审稿时长

2.1 months

期刊介绍： DRM is a leading international journal that publishes new fundamental and applied research on all forms of diamond, the integration of diamond with other advanced materials and development of technologies exploiting diamond. The synthesis, characterization and processing of single crystal diamond, polycrystalline films, nanodiamond powders and heterostructures with other advanced materials are encouraged topics for technical and review articles. In addition to diamond, the journal publishes manuscripts on the synthesis, characterization and application of other related materials including diamond-like carbons, carbon nanotubes, graphene, and boron and carbon nitrides. Articles are sought on the chemical functionalization of diamond and related materials as well as their use in electrochemistry, energy storage and conversion, chemical and biological sensing, imaging, thermal management, photonic and quantum applications, electron emission and electronic devices. The International Conference on Diamond and Carbon Materials has evolved into the largest and most well attended forum in the field of diamond, providing a forum to showcase the latest results in the science and technology of diamond and other carbon materials such as carbon nanotubes, graphene, and diamond-like carbon. Run annually in association with Diamond and Related Materials the conference provides junior and established researchers the opportunity to exchange the latest results ranging from fundamental physical and chemical concepts to applied research focusing on the next generation carbon-based devices.