Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO2 and CeO2)

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} div.type-section h2 { font-size: 20px; line-height: 26px; font-weight: 300; } div.type-section h3 { margin-left: 15px; margin-bottom: 0px; font-weight: 300; } .journal-tabs .tab-title.active a { } </style> <link rel="stylesheet" href="https://pub.mdpi-res.com/assets/css/slick.css?f38b2db10e01b157?1732286508"> <meta name="title" content="Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO2 and CeO2)"> <meta name="description" content="The accumulation of greenhouse gasses (CH4 and CO2) results in an increase in the temperature of the atmosphere. The conversion of greenhouse gasses into chemicals and fuels with high added value benefits not only the environment but also energy development. A promising and well-studied process is the reforming of methane, where CH4 and CO2 are converted into syngas (CO and H2). However, catalysts hinder the development of the process. In this paper, we investigate the conversion of CH4 and CO2 into syngas using a thermal conversion method. The catalysis performance was evaluated by reforming methane. Ni-based catalysts were prepared by different methods. All prepared catalysts were characterized (XRD, HRTEM et al.), and the process of reforming carbon dioxide–methane was carried out in a fixed bed reactor under atmospheric pressure and a high temperature. Ni(M) @CeO2 is one of the most popular options due to the role of CeO2. The deposition of coke in Ni-based catalysts was investigated." > <link rel="image_src" href="https://pub.mdpi-res.com/img/journals/nanomaterials-logo.png?8600e93ff98dbf14" > <meta name="dc.title" content="Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO2 and CeO2)"> <meta name="dc.creator" content="Derun Hua"> <meta name="dc.creator" content="Jian Li"> <meta name="dc.creator" content="Xiaowen Guo"> <meta name="dc.creator" content="Xinning Lu"> <meta name="dc.creator" content="Hao Ding"> <meta name="dc.creator" content="Rengui He"> <meta name="dc.type" content="Article"> <meta name="dc.source" content="Nanomaterials 2024, Vol. 14, Page 1877"> <meta name="dc.date" content="2024-11-22"> <meta name ="dc.identifier" content="10.3390/nano14231877"> <meta name="dc.publisher" content="Multidisciplinary Digital Publishing Institute"> <meta name="dc.rights" content="http://creativecommons.org/licenses/by/3.0/"> <meta name="dc.format" content="application/pdf" > <meta name="dc.language" content="en" > <meta name="dc.description" content="The accumulation of greenhouse gasses (CH4 and CO2) results in an increase in the temperature of the atmosphere. The conversion of greenhouse gasses into chemicals and fuels with high added value benefits not only the environment but also energy development. A promising and well-studied process is the reforming of methane, where CH4 and CO2 are converted into syngas (CO and H2). However, catalysts hinder the development of the process. In this paper, we investigate the conversion of CH4 and CO2 into syngas using a thermal conversion method. The catalysis performance was evaluated by reforming methane. Ni-based catalysts were prepared by different methods. All prepared catalysts were characterized (XRD, HRTEM et al.), and the process of reforming carbon dioxide–methane was carried out in a fixed bed reactor under atmospheric pressure and a high temperature. Ni(M) @CeO2 is one of the most popular options due to the role of CeO2. The deposition of coke in Ni-based catalysts was investigated." > <meta name="dc.subject" content="reforming" > <meta name="dc.subject" content="Core@Shell material" > <meta name="dc.subject" content="MOF" > <meta name ="prism.issn" content="2079-4991"> <meta name ="prism.publicationName" content="Nanomaterials"> <meta name ="prism.publicationDate" content="2024-11-22"> <meta name ="prism.volume" content="14"> <meta name ="prism.number" content="23"> <meta name ="prism.section" content="Article" > <meta name ="prism.startingPage" content="1877" > <meta name="citation_issn" content="2079-4991"> <meta name="citation_journal_title" content="Nanomaterials"> <meta name="citation_publisher" content="Multidisciplinary Digital Publishing Institute"> <meta name="citation_title" content="Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO2 and CeO2)"> <meta name="citation_publication_date" content="2024/1"> <meta name="citation_online_date" content="2024/11/22"> <meta name="citation_volume" content="14"> <meta name="citation_issue" content="23"> <meta name="citation_firstpage" content="1877"> <meta name="citation_author" content="Hua, Derun"> <meta name="citation_author" content="Li, Jian"> <meta name="citation_author" content="Guo, Xiaowen"> <meta name="citation_author" content="Lu, Xinning"> <meta name="citation_author" content="Ding, Hao"> <meta name="citation_author" content="He, Rengui"> <meta name="citation_doi" content="10.3390/nano14231877"> <meta name="citation_id" content="mdpi-nano14231877"> <meta name="citation_abstract_html_url" content="https://www.mdpi.com/2079-4991/14/23/1877"> <meta name="citation_pdf_url" content="https://www.mdpi.com/2079-4991/14/23/1877/pdf?version=1732271506"> <link rel="alternate" type="application/pdf" title="PDF Full-Text" href="https://www.mdpi.com/2079-4991/14/23/1877/pdf?version=1732271506"> <meta name="fulltext_pdf" content="https://www.mdpi.com/2079-4991/14/23/1877/pdf?version=1732271506"> <meta name="citation_fulltext_html_url" content="https://www.mdpi.com/2079-4991/14/23/1877/htm"> <link rel="alternate" type="text/html" title="HTML Full-Text" href="https://www.mdpi.com/2079-4991/14/23/1877/htm"> <meta name="fulltext_html" content="https://www.mdpi.com/2079-4991/14/23/1877/htm"> <link rel="alternate" type="text/xml" title="XML Full-Text" href="https://www.mdpi.com/2079-4991/14/23/1877/xml"> <meta name="fulltext_xml" content="https://www.mdpi.com/2079-4991/14/23/1877/xml"> <meta name="citation_xml_url" content="https://www.mdpi.com/2079-4991/14/23/1877/xml"> <meta name="twitter:card" content="summary" /> <meta name="twitter:site" content="@MDPIOpenAccess" /> <meta name="twitter:image" content="https://pub.mdpi-res.com/img/journals/nanomaterials-logo-social.png?8600e93ff98dbf14" /> <meta property="fb:app_id" content="131189377574"/> <meta property="og:site_name" content="MDPI"/> <meta property="og:type" content="article"/> <meta property="og:url" content="https://www.mdpi.com/2079-4991/14/23/1877" /> <meta property="og:title" content="Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO2 and CeO2)" /> <meta property="og:description" content="The accumulation of greenhouse gasses (CH4 and CO2) results in an increase in the temperature of the atmosphere. The conversion of greenhouse gasses into chemicals and fuels with high added value benefits not only the environment but also energy development. A promising and well-studied process is the reforming of methane, where CH4 and CO2 are converted into syngas (CO and H2). However, catalysts hinder the development of the process. In this paper, we investigate the conversion of CH4 and CO2 into syngas using a thermal conversion method. The catalysis performance was evaluated by reforming methane. Ni-based catalysts were prepared by different methods. All prepared catalysts were characterized (XRD, HRTEM et al.), and the process of reforming carbon dioxide–methane was carried out in a fixed bed reactor under atmospheric pressure and a high temperature. Ni(M) @CeO2 is one of the most popular options due to the role of CeO2. The deposition of coke in Ni-based catalysts was investigated." /> <meta property="og:image" content="https://pub.mdpi-res.com/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001-550.jpg?1732271615" /> <link rel="alternate" type="application/rss+xml" title="MDPI Publishing - Latest articles" href="https://www.mdpi.com/rss"> <meta name="google-site-verification" content="PxTlsg7z2S00aHroktQd57fxygEjMiNHydKn3txhvwY"> <meta name="facebook-domain-verification" content="mcoq8dtq6sb2hf7z29j8w515jjoof7" /> <script id="Cookiebot" data-cfasync="false" src="https://consent.cookiebot.com/uc.js" data-cbid="51491ddd-fe7a-4425-ab39-69c78c55829f" type="text/javascript" async></script>  <script type="text/plain" data-cookieconsent="statistics"> (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start': new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0], j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src= 'https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f); 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</div> </div> </div> <div class="bib-identity" style="margin-bottom: 10px;"> <em>Nanomaterials</em> <b>2024</b>, <em>14</em>(23), 1877; <a href="https://doi.org/10.3390/nano14231877">https://doi.org/10.3390/nano14231877</a> </div> <div class="pubhistory" style="font-weight: bold; padding-bottom: 10px;"> <span style="display: inline-block">Submission received: 14 August 2024</span> / <span style="display: inline-block">Revised: 18 September 2024</span> / <span style="display: inline-block">Accepted: 25 September 2024</span> / <span style="display: inline-block">Published: 22 November 2024</span> </div> <div class="highlight-box1"> <div class="download"> <a class="button button--color-inversed button--drop-down" data-dropdown="drop-download-1527043" aria-controls="drop-supplementary-1527043" aria-expanded="false"> Download <i class="material-icons">keyboard_arrow_down</i> </a> <div id="drop-download-1527043" class="f-dropdown label__btn__dropdown label__btn__dropdown--button" 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H<sub>2</sub> and CO, (<b>d</b>): effect of reaction temperature).</p> "> </a> <a href="https://pub.mdpi-res.com/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004.png?1732271620" title=" <strong>Figure 4</strong><br/> <p>Effects of core and shell of catalysts on carbon deposit.</p> "> </a> <a href="https://pub.mdpi-res.com/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005.png?1732271621" title=" <strong>Figure 5</strong><br/> <p>X-ray diffractograms of four reduced catalysts.</p> "> </a> <a href="https://pub.mdpi-res.com/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006.png?1732271623" title=" <strong>Figure 6</strong><br/> <p>TGA of spent catalysts (Ni@SiO<sub>2</sub>, Ni(M)@SiO<sub>2</sub>, Ni@CeO<sub>2</sub>, and Ni(M)@CeO<sub>2</sub>).</p> "> </a> <a href="https://pub.mdpi-res.com/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007.png?1732271624" title=" <strong>Figure 7</strong><br/> <p>Ni 2p and Ce 3d XPS spectra of spent Ni@CeO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> catalysts. ((<b>A</b>): Ni 2p, (<b>B</b>): Ce 3d).</p> "> </a> </div> <a class="button button--color-inversed" href="/2079-4991/14/23/1877/review_report">Review Reports</a> <a class="button button--color-inversed" href="/2079-4991/14/23/1877/notes">Versions Notes</a> </div> </div> <div class="responsive-moving-container small hidden" data-id="article-counters" style="margin-top: 15px;"></div> <div class="html-dynamic"> <section> <div class="art-abstract art-abstract-new in-tab hypothesis_container"> <p> <div><section class="html-abstract" id="html-abstract"> <h2 id="html-abstract-title">Abstract</h2><b>:</b> <div class="html-p">The accumulation of greenhouse gasses (CH<sub>4</sub> and CO<sub>2</sub>) results in an increase in the temperature of the atmosphere. The conversion of greenhouse gasses into chemicals and fuels with high added value benefits not only the environment but also energy development. A promising and well-studied process is the reforming of methane, where CH<sub>4</sub> and CO<sub>2</sub> are converted into syngas (CO and H<sub>2</sub>). However, catalysts hinder the development of the process. In this paper, we investigate the conversion of CH<sub>4</sub> and CO<sub>2</sub> into syngas using a thermal conversion method. The catalysis performance was evaluated by reforming methane. Ni-based catalysts were prepared by different methods. All prepared catalysts were characterized (XRD, HRTEM et al.), and the process of reforming carbon dioxide–methane was carried out in a fixed bed reactor under atmospheric pressure and a high temperature. Ni(M) @CeO<sub>2</sub> is one of the most popular options due to the role of CeO<sub>2</sub>. The deposition of coke in Ni-based catalysts was investigated.</div> </section> <div id="html-keywords"> <div class="html-gwd-group"><div id="html-keywords-title">Keywords: </div><a href="/search?q=reforming">reforming</a>; <a href="/search?q=Core%40Shell+material">Core@Shell material</a>; <a href="/search?q=MOF">MOF</a></div> <div> </div> </div> </div> </p> </div> </section> </div> <div class="hypothesis_container"> <ul class="menu html-nav" data-prev-node="#html-quick-links-title"> </ul> <div class="html-body"> <section id='sec1-nanomaterials-14-01877' type='intro'><h2 data-nested='1'> 1. Introduction</h2><div class='html-p'>The continuous consumption of non-renewable sources results in an increase in CO<sub>2</sub> in the atmosphere, which results in the destruction of balance in the natural climate. Therefore, mitigating CO<sub>2</sub> pollution has become an outstanding area of research. In view of this, researchers have investigated several strategies based on the development of catalysts. The catalytic conversion of CO<sub>2</sub> into value-added fuels and chemicals has become one of the most practical CO<sub>2</sub> mitigation approaches. So far, research on catalytic CO<sub>2</sub> conversion has focused on electrochemical [<a href="#B1-nanomaterials-14-01877" class="html-bibr">1</a>] and thermochemical approaches [<a href="#B2-nanomaterials-14-01877" class="html-bibr">2</a>]. Apart from carbon dioxide, the high emission of CH<sub>4</sub> is responsible for the temperature increase; therefore, it is urgent to control these emissions and convert CO<sub>2</sub> and CH<sub>4</sub> into other useful substances. Against this background, the dry reforming of CH<sub>4</sub> and CO<sub>2</sub> has attracted much attention because syngas is a prospective feedstock to produce chemical materials (see <a href="#nanomaterials-14-01877-f001" class="html-fig">Figure 1</a>).</div><div class='html-p'>The dry reforming of methane (DRM, <math display='inline'><semantics> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>+</mo> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> <mo>=</mo> <mn>2</mn> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> <mo>+</mo> <mn>2</mn> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math>) is one of the most promising and well-researched processes to mitigate global warming as it simultaneously converts the two most abundant greenhouse gasses (CH<sub>4</sub> and CO<sub>2</sub>) into syngas (CO and H<sub>2</sub>), which is used not only as a gaseous fuel but also as a feedstock for high-value production, such as methyl alcohol and ethylene [<a href="#B3-nanomaterials-14-01877" class="html-bibr">3</a>,<a href="#B4-nanomaterials-14-01877" class="html-bibr">4</a>].</div><div class='html-p'>In this process, the deposition of carbon on the surface and the sintering of active metal particles are two major problems that lead to deactivation [<a href="#B5-nanomaterials-14-01877" class="html-bibr">5</a>]. Despite precious metal-based catalysts are highly active, they undergo less coking and are high stable, they are not available and have high cost [<a href="#B6-nanomaterials-14-01877" class="html-bibr">6</a>,<a href="#B7-nanomaterials-14-01877" class="html-bibr">7</a>]. In comparison, Ni-based catalysts are more promising candidates for the DRM reaction as they are easily accessible.</div><div class='html-p'>Ni-based catalysts, with their fast conversion rates, availability, and low cost, are industrially accepted for dry reforming reactions [<a href="#B8-nanomaterials-14-01877" class="html-bibr">8</a>] and frequently studied. Apanee et al. investigated the catalytic performance of Ni based on zeolites; the authors reported that Ni/zeolite Y showed better catalytic performance [<a href="#B9-nanomaterials-14-01877" class="html-bibr">9</a>]. Kaydouh et al. reported that a high dispersion of nickel and cerium inside SBA-15 was achieved using the “two-solvent” deposition method [<a href="#B10-nanomaterials-14-01877" class="html-bibr">10</a>]. It follows that the preparation method and carriers have a direct influence on the dispersion of nickel species. Despite their low cost and catalytic activity, Ni-based catalysts are more susceptible to deactivation by carbon deposition than noble metal-based catalysts [<a href="#B5-nanomaterials-14-01877" class="html-bibr">5</a>,<a href="#B11-nanomaterials-14-01877" class="html-bibr">11</a>]. Therefore, researchers have recently tried to improve the catalytic properties of Ni-based catalysts. Bimetallic catalysts show better performance than Ni-based catalysts [<a href="#B12-nanomaterials-14-01877" class="html-bibr">12</a>,<a href="#B13-nanomaterials-14-01877" class="html-bibr">13</a>,<a href="#B14-nanomaterials-14-01877" class="html-bibr">14</a>]. The catalytic performance of catalysts has also been improved by doping promoters [<a href="#B15-nanomaterials-14-01877" class="html-bibr">15</a>,<a href="#B16-nanomaterials-14-01877" class="html-bibr">16</a>], which create new active sites and prevent carbon formation [<a href="#B17-nanomaterials-14-01877" class="html-bibr">17</a>,<a href="#B18-nanomaterials-14-01877" class="html-bibr">18</a>].</div><div class='html-p'>In addition, the performance of the catalysts was improved by inhibiting carbon deposition [<a href="#B5-nanomaterials-14-01877" class="html-bibr">5</a>,<a href="#B17-nanomaterials-14-01877" class="html-bibr">17</a>,<a href="#B19-nanomaterials-14-01877" class="html-bibr">19</a>]. It was reported that cerium oxide can prevent the carbon deposition of catalysts. The reducibility and the total basicity of the catalysts were improved by the addition of Ce, which was responsible for the improvement in the catalytic activity [<a href="#B2-nanomaterials-14-01877" class="html-bibr">2</a>,<a href="#B18-nanomaterials-14-01877" class="html-bibr">18</a>,<a href="#B20-nanomaterials-14-01877" class="html-bibr">20</a>,<a href="#B21-nanomaterials-14-01877" class="html-bibr">21</a>,<a href="#B22-nanomaterials-14-01877" class="html-bibr">22</a>].</div><div class='html-p'>Recently, much attention has been paid to materials with core/shell structures in which the active metals are confined to narrow regions and can effectively hinder the aggregation of active nanoparticles by the confinement effect of the shell [<a href="#B23-nanomaterials-14-01877" class="html-bibr">23</a>,<a href="#B24-nanomaterials-14-01877" class="html-bibr">24</a>]. Ji et al. reported that a novel Ni@SiO<sub>2</sub> yolk–shell nanoreactor is used as a model catalyst for the steam methane reforming reaction and is superior to Ni/MCF catalysts and comparable to modern commercial catalysts [<a href="#B23-nanomaterials-14-01877" class="html-bibr">23</a>]. Kang et al. synthesized Ni supported on Al<sub>2</sub>O<sub>3</sub> and MgO–Al<sub>2</sub>O<sub>3</sub> with core/shell structures with stability [<a href="#B25-nanomaterials-14-01877" class="html-bibr">25</a>]. Li et al. reported that Ni nanoparticles (NPs) with a narrow size distribution was encapsulated by meso- and microporous silica [<a href="#B26-nanomaterials-14-01877" class="html-bibr">26</a>]. </div><div class='html-p'>The great attention paid to core/shell structures is due to the controllability of the components of the shell. It is difficult to synthesize such composites, and intensive research is still ongoing [<a href="#B27-nanomaterials-14-01877" class="html-bibr">27</a>,<a href="#B28-nanomaterials-14-01877" class="html-bibr">28</a>].</div><div class='html-p'>In this work, we aim to investigate the effects of reaction conditions on the performance of catalysts and coke. We are interested in elucidating the role of Ce in the dry reforming of methane, especially its influence on carbonaceous deposition.</div></section><section id='sec2-nanomaterials-14-01877' type='results'><h2 data-nested='1'> 2. Results and Discussion</h2><section id='sec2dot1-nanomaterials-14-01877' type=''><h4 class='html-italic' data-nested='2'> 2.1. Characterization of Catalysts</h4><div class='html-p'>The TEM images show that Ni nanoparticles with different sizes were randomly distributed (<a href="#nanomaterials-14-01877-f002" class="html-fig">Figure 2</a>). In particular, the size of the relatively larger Ni particles was about 20 nm, and that of the relatively smaller Ni particles was about 7 nm, and the Ni particle size distribution centered at 10 nm. A Ni (110) crystal plane corresponding to a lattice spacing of about 0.182 nm was found.</div></section><section id='sec2dot2-nanomaterials-14-01877' type=''><h4 class='html-italic' data-nested='2'> 2.2. Test of Catalysts</h4><div class='html-p'>The dry reforming of methane and carbon dioxide is not spontaneous below 400 °C and at atmospheric pressure as it is a highly endothermic reaction; therefore, the reaction temperature is set above 700 °C.</div><div class='html-p'>An effect of the pretreatment temperature on the catalysts was shown in <a href="#nanomaterials-14-01877-f003" class="html-fig">Figure 3</a>. The observed catalytic conversions generally increased with the pretreatment temperature, and the maximum conversion was observed at 700 °C. Then, the conversions decreased with the increase in the pretreatment temperature, indicating that Ni<sup>x+</sup> can be completely reduced to Ni<sup>0</sup> below 700 °C; moreover, the Ni particles were aggregated above 700 °C. In general, the H<sub>2</sub>/CO ratio seems to be related to the activity of the catalysts. As confirmed in the current study, the H<sub>2</sub>/CO ratio depends on the degree of Ni reduction. The H<sub>2</sub>/CO ratio was found to be less than 1, which is due to the occurrence of the reverse water–gas shift reaction (<math display='inline'><semantics> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>=</mo> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> <mo>+</mo> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mi mathvariant="normal">O</mi> </mrow> </semantics></math>).</div><div class='html-p'>The stability of four catalysts was determined at 750 °C. <a href="#nanomaterials-14-01877-f004" class="html-fig">Figure 4</a> shows the conversion of methane, carbon dioxide, and the molar ratio H<sub>2</sub>/CO with time on stream (9 h) over four catalysts. As can be seen in the figure, there was no change in conversion for three catalysts (Ni(M)@SiO<sub>2</sub>, Ni@CeO<sub>2</sub>, and Ni(M)@CeO<sub>2</sub>), indicating that the three catalysts hold good duration, but there was an outstanding change in the H<sub>2</sub>/CO ratio for Ni@SiO<sub>2</sub>. The Ni@SiO<sub>2</sub> catalyst showed a much worse duration than the others, while Ni(M)@CeO<sub>2</sub> exhibited the best stability among the four catalysts. In addition, we found that the conversion of CO<sub>2</sub> was higher than that of methane for the equation <math display='inline'><semantics> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>=</mo> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> <mo>+</mo> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mi mathvariant="normal">O</mi> </mrow> </semantics></math>. After a duration of 9 h, the CH<sub>4</sub> and CO<sub>2</sub> conversions showed analogous trends and remained stable, while the H<sub>2</sub>/CO molar ratio of the Ni@SiO<sub>2</sub> catalyst decreased markedly from 0.86 to 0.8. According to the above results, the performance of the catalysts was affected by the pretreatment temperature and the composition of the shell. According to [<a href="#B29-nanomaterials-14-01877" class="html-bibr">29</a>], the decomposition of methane and the Boudouard reaction are the main causes for the formation of carbon during the dry reforming reaction. At low temperatures and a high pressure, the Boudouard reaction dominates for the exothermic reaction and is a lower amount of gas moles. In contrast, at a high temperature and a low pressure, methane cracking dominates for the endothermic reaction and the formation of more gas moles. In this study, carbon deposition from methane cracking was predominant.</div><div class='html-p'><a href="#nanomaterials-14-01877-f005" class="html-fig">Figure 5</a> shows the XRD data of the four samples prepared with various methods. As can be seen in <a href="#nanomaterials-14-01877-f005" class="html-fig">Figure 5</a>, the peak at 43.3° (visible in <a href="#nanomaterials-14-01877-f005" class="html-fig">Figure 5</a>) was identified for all samples and assigned to (202) NiO nanocrystals. The peak at 37.2° was only identified for Ni@SiO<sub>2</sub> and Ni@CeO<sub>2</sub> and assigned to (021) NiO nanocrystals. Ni° was oxidized to Ni<sup>2+</sup> after the reaction. In addition, the peak at 37.2° was not identified for Ni(M) @SiO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> prepared with MOFs (<a href="#app1-nanomaterials-14-01877" class="html-app">Figure S1</a>), which can be attributed to the low nickel content or high dispersion of NiO particles. The peaks at 44.5°, 51.8°, and 76.3° refer to the Ni<sup>0</sup> species. The XRD patterns of as-synthesized Ni(M)@SiO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> show the existence of a distinct fluorite-like oxide structure of CeO<sub>2</sub> (JCPDS 34-0394, space group Fm3m). There are eight diffraction peaks centered at 28.5°, 33.1°, 47.5°, 56.3°, 59.1°, 69.4°, 76.7°, and 79.1°. These peaks correspond to (111), (200), (220), (311), (222), (400), (331), (420), and (422) of the fcc structure, respectively [<a href="#B30-nanomaterials-14-01877" class="html-bibr">30</a>].</div><div class='html-p'>The carbon deposition of the catalysts was determined by a thermal gravity analysis (TGA). As can be seen in <a href="#nanomaterials-14-01877-f006" class="html-fig">Figure 6</a>, there is no mass-loss step associated with the evaporation of water for the four catalysts. Weight loss was found above 150 °C and decreased as follows: Ni@SiO<sub>2</sub> > Ni(M)@SiO<sub>2</sub> > Ni@CeO<sub>2</sub> > Ni(M)@CeO<sub>2</sub>. The quantitative coke contents of the spent Ni@SiO<sub>2</sub>, Ni(M)@SiO<sub>2</sub>, Ni@CeO<sub>2</sub>, and Ni(M)@CeO<sub>2</sub> were determined to be 12.41, 8.26, 5.11, and 1.72 wt.%, respectively. Therefore, carbon deposition over Ni@CeO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> is effectively inhibited for the redox nature of the CeO<sub>2</sub> shell.</div><div class='html-p'>The surface structure of the reforming catalyst changed after carbonization. Therefore, XPS characterization was performed. As shown in <a href="#nanomaterials-14-01877-f007" class="html-fig">Figure 7</a>, the Ni 2p (<a href="#nanomaterials-14-01877-f007" class="html-fig">Figure 7</a>A) and Ce 3d (<a href="#nanomaterials-14-01877-f007" class="html-fig">Figure 7</a>B) XPS spectra of the spent Ni@CeO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> are shown. The peak at 856.6 eV and the satellite peak at 861 eV were attributed to Ni<sup>2+</sup> because Ni<sup>0</sup> was oxidized to Ni<sup>2+</sup> after the reaction. The peak at 852.4 eV and 859.6 eV was attributed to Ni<sup>0</sup>. According to the literature [<a href="#B31-nanomaterials-14-01877" class="html-bibr">31</a>,<a href="#B32-nanomaterials-14-01877" class="html-bibr">32</a>], the spectra were deconvoluted into many peaks, Ce 3d<sub>5/2</sub> was tagged as v contributions, and Ce 3d<sub>3/2</sub> was tagged as u contributions. The u″, u, and v‴ peaks were attributed to Ce<sup>4+</sup>, while the u′ and u<sup>0</sup> peaks were attributed to Ce<sup>3+</sup>. The coexistence of Ce<sup>4+</sup> and Ce<sup>3+</sup> reveals the special property (redox) of the CeO<sub>2</sub> shell, which facilitates the oxidation of the deposited carbon with the participation of lattice oxygen. CeO<sub>2</sub> is a suitable material for reforming methane due to its high specific surface area and abundant oxygen vacancies.</div></section></section><section id='sec3-nanomaterials-14-01877' type=''><h2 data-nested='1'> 3. Experimental Procedure</h2><section id='sec3dot1-nanomaterials-14-01877' type=''><h4 class='html-italic' data-nested='2'> 3.1. Catalyst Synthesis </h4><div class='html-p'>All used chemicals were not further purified.</div><dl class='html-order'><dt id=''>(1)</dt><dd><div class='html-p'>Synthesis of Ni nanoparticles [<a href="#B33-nanomaterials-14-01877" class="html-bibr">33</a>]</div></dd></dl><div class='html-p'>Ni(acac)<sub>2</sub> (1.00 g; 3.90 mmol) was added to 39.0 mmol of oleylamine (10.4 g; 5 equiv) and 3.12 mmol of trioctylphosphine (1.15 g, 0.4 equiv). The mixture was degassed at 100 °C and then heated at 220 °C for 2 h under a nitrogen atmosphere. The mixture was cooled to room temperature and centrifuged after adding 40 mL of acetone to obtain a black product. The nanoparticles were redispersed in a mixture of hexane and ethanol (molar ratio of 3:1).</div><dl class='html-order'><dt id=''>(2)</dt><dd><div class='html-p'>Synthesis of Ni@CeO<sub>2</sub>(SiO<sub>2</sub>) [<a href="#B34-nanomaterials-14-01877" class="html-bibr">34</a>]</div></dd></dl><div class='html-p'>Ni nanoparticles were coated with silicon dioxide and cerium dioxide. The suspension of Ni nanoparticles (15 mL) was mixed with 20 mL P123 and 3 mL ammonia (30 wt%) to form a microemulsion and stirred for 60 min. An amount of 1.5 mL of TEOS or cerium nitrate (2 mL; 1 mol/L) was added using a syringe pump with a flow rate of 1 mL·h<sup>−1</sup>. After 96 h of reaction, the Ni@SiO<sub>2</sub> nanoparticles (Ni@CeO<sub>2</sub> nanoparticles) were separated and washed using ethanol, dried in air, and calcined at 650 °C for 3 h. </div><dl class='html-order'><dt id=''>(3)</dt><dd><div class='html-p'>Synthesis of Ni-BTC [<a href="#B35-nanomaterials-14-01877" class="html-bibr">35</a>]</div></dd></dl><div class='html-p'>1,3,5-Benzenetricarboxylic acid (0.105 g) and sodium hydroxide (0.06 g) were dissolved in 30 mL of deionized water; the resulting mixture was stirred at room temperature for 30 min. Then, Ni (NO<sub>3</sub>)<sub>2</sub>∙6H<sub>2</sub>O (0.29 g) was added to the above solution and stirred well. Finally, the reaction mixture was added to a 50 mL stainless steel reactor, sealed, and heated in an oven to 130 °C for 72 h. After the reaction, it was naturally cooled to room temperature, and the blue Ni-BTC crystals were collected from the final reaction mixture by filtration and air-dried at room temperature. </div><dl class='html-order'><dt id=''>(4)</dt><dd><div class='html-p'>Synthesis of Ni(M)@CeO<sub>2</sub> and Ni(M)@SiO<sub>2</sub> based on metal–organic frameworks (MOFs) [<a href="#B36-nanomaterials-14-01877" class="html-bibr">36</a>,<a href="#B37-nanomaterials-14-01877" class="html-bibr">37</a>]</div></dd></dl><div class='html-p'>MOF powder (100 mg) was dispersed in ammonium hydroxide (5 wt%) aqueous solution. Then, a certain amount of octadecyl trimethoxy silane or cerium nitrate was added to the above mixture with a micropump (2 mL/h). The above mixture was kept at 80 °C for 72 h, MOF@CeO<sub>2</sub> and MOF@SiO<sub>2</sub> were synthesized and calcined at 600 °C, and Ni(M) @CeO<sub>2</sub> and Ni(M)SiO<sub>2</sub> were obtained. </div></section><section id='sec3dot2-nanomaterials-14-01877' type=''><h4 class='html-italic' data-nested='2'> 3.2. Characterization of Catalyst</h4><div class='html-p'>The X-ray powder diffractograms of the catalysts were recorded with a Bruker D8 ADVACE diffractometer using CuKa (1.5406 Å) radiation in the range of 5–85° with a scanning rate of 1°/min. High-resolution transition electron microscopy (HR-TEM) images were obtained with a Tecnai G2F20 Super-twin (FEI) microscope (FEI Corporation, Hillsboro, OR, USA). Thermogravimetric analysis (TGA) was carried out on a TGAQ50 (TA INSTRUMENTS). To perform the TGA test, 4 mg of spent catalyst was loaded, and the temperature was increased from 25 to 800 °C with a temperature ramp of 10 °C·min<sup>−1</sup> in an air flow.</div></section><section id='sec3dot3-nanomaterials-14-01877' type=''><h4 class='html-italic' data-nested='2'> 3.3. Evaluation of Catalytic Performance </h4><div class='html-p'>The evaluation of catalytic performance was carried out in a fixed bed quartz reactor with an inner diameter of 5 mm. Typically, 100 mg of catalysts was loaded into the reactor and reduced with mixed gas (H<sub>2</sub>/N<sub>2</sub> = 1:5; 10 mL/min) for 30 min at 650 °C. In all studies, the feed gas was used with a constant of V(CH<sub>4</sub>):V (CO<sub>2</sub>):V (Ar) = 1:1:2, where Ar was used as the carrier gas. The catalytic reaction was evaluated under GHSV = 6000 mL·g<sup>−1</sup>⋅h<sup>−1</sup>. The composition of exhaust gas was determined using an online GC system (Tian Mei GC-7980, Quanzhou, China) equipped with a TDX-01 column and a TCD. The conversion (<math display='inline'><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> </mrow> </msub> <mtext> </mtext> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">d</mi> <mtext> </mtext> <msub> <mrow> <mi mathvariant="normal">C</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> </mrow> </semantics></math>) and selectivity (<math display='inline'><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">S</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> </msub> <mtext> </mtext> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">d</mi> <mtext> </mtext> <msub> <mrow> <mi mathvariant="normal">S</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> </mrow> </semantics></math>) were calculated using the following equations:<div class='html-disp-formula-info' id='FD1-nanomaterials-14-01877'> <div class='f'> <math display='block'><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> </mrow> </msub> <mo>=</mo> <mstyle scriptlevel="0" displaystyle="true"> <mfrac> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> <mo>−</mo> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">u</mi> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> </mrow> </mfrac> </mstyle> <mo>×</mo> <mn>100</mn> <mi mathvariant="normal">%</mi> </mrow> </semantics></math> </div> <div class='l'> <label >(1)</label> </div> </div><div class='html-disp-formula-info' id='FD2-nanomaterials-14-01877'> <div class='f'> <math display='block'><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> <mo>=</mo> <mstyle scriptlevel="0" displaystyle="true"> <mfrac> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> <mo>−</mo> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">u</mi> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> </mrow> </mfrac> </mstyle> <mo>×</mo> <mn>100</mn> <mi mathvariant="normal">%</mi> </mrow> </semantics></math> </div> <div class='l'> <label >(2)</label> </div> </div><div class='html-disp-formula-info' id='FD3-nanomaterials-14-01877'> <div class='f'> <math display='block'><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">S</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> </msub> <mo>=</mo> <mstyle scriptlevel="0" displaystyle="true"> <mfrac> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> <mo>,</mo> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">u</mi> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> </mrow> </mfrac> </mstyle> <mo>×</mo> <mn>100</mn> <mi mathvariant="normal">%</mi> </mrow> </semantics></math> </div> <div class='l'> <label >(3)</label> </div> </div><div class='html-disp-formula-info' id='FD4-nanomaterials-14-01877'> <div class='f'> <math display='block'><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">S</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> <mo>=</mo> <mstyle scriptlevel="0" displaystyle="true"> <mfrac> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">u</mi> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>4</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> </mrow> </mfrac> </mstyle> <mo>×</mo> <mn>100</mn> <mi mathvariant="normal">%</mi> </mrow> </semantics></math> </div> <div class='l'> <label >(4)</label> </div> </div><div class='html-disp-formula-info' id='FD5-nanomaterials-14-01877'> <div class='f'> <math display='block'><semantics> <mrow> <mstyle scriptlevel="0" displaystyle="true"> <mfrac> <mrow> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> </mrow> </mfrac> </mstyle> <mo>=</mo> <mstyle scriptlevel="0" displaystyle="true"> <mfrac> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mo>,</mo> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">u</mi> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">F</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">O</mi> <mo>,</mo> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">u</mi> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> </mfrac> </mstyle> </mrow> </semantics></math> </div> <div class='l'> <label >(5)</label> </div> </div></div></section></section><section id='sec4-nanomaterials-14-01877' type='conclusions'><h2 data-nested='1'> 4. Conclusions</h2><div class='html-p'>The aim of this project was to investigate the suitability of Ni@M catalysts with different compositions and preparation methods as catalysts for dry reforming. It was important to show the effects of the shell on the activity and stability of the catalysts.</div><div class='html-p'>Therefore, various catalysts, such as Ni@SiO<sub>2</sub>, Ni(M)@SiO<sub>2</sub>, Ni@CeO<sub>2</sub>, and Ni(M)@CeO<sub>2</sub>, were synthesized and characterized using numerous technologies (HRTEM, XRD, etc.). The characterized results reveal the structures of the catalysts.</div><div class='html-p'>In summary, the Ni(M)@/CeO<sub>2</sub> catalyst exhibited better stability than the other catalysts. The CO<sub>2</sub> conversion and CH<sub>4</sub> conversion were 85% and 87%, respectively. The TGA profile confirms that less carbon was deposited on the Ni(M)@CeO<sub>2</sub> catalyst. The XPS characterizations show that the Ni(M)@CeO<sub>2</sub> catalyst possessed a stronger redox property and enriched surface basicity, which may improve the coke resistance of the Ni(M)@CeO<sub>2</sub> catalyst.</div></section> </div> <div class="html-back"> <section><section id='app1-nanomaterials-14-01877' type=''><h2 data-nested='1'> Supplementary Materials</h2><div class='html-p'>The following supporting information can be downloaded at: <a href='https://www.mdpi.com/article/10.3390/nano14231877/s1' target='_blank' rel="noopener noreferrer">https://www.mdpi.com/article/10.3390/nano14231877/s1</a>, Figure S1: XRD patterns of MOFs simulation and experiment. Figure S2: Tem of Ni@CeO<sub>2</sub>(M).</div></section></section><section class='html-notes'><h2 >Author Contributions</h2><div class='html-p'>Conceptualization, D.H., J.L. and H.D.; methodology, X.G.; software, R.H.; validation, D.H. and H.D.; formal analysis, D.H. and J.L.; investigation, D.H.; resources, D.H.; data curation, H.D.; writing—original draft preparation, D.H. and H.D.; writing—review and editing, D.H.; visualization, X.L.; supervision, D.H.; project administration, D.H.; funding acquisition, D.H. All authors have read and agreed to the published version of the manuscript.</div></section><section class='html-notes'><h2>Funding</h2><div class='html-p'>This project was funded by the Natural Science Foundation of the Jiangxi Provincial Department of Education (GJJ2201229 and GJJ211421).</div></section><section class='html-notes'><h2 >Data Availability Statement</h2><div class='html-p'>All relevant data are contained within this manuscript and its <a href="#app1-nanomaterials-14-01877" class="html-app">Supplementary Files</a>.</div></section><section class='html-notes'><h2 >Conflicts of Interest</h2><div class='html-p'>The authors declare no conflict of interest.</div></section><section id='html-references_list'><h2>References</h2><ol class='html-xx'><li id='B1-nanomaterials-14-01877' class='html-x' data-content='1.'>Yuan, Y.; Zhang, Y.; Li, H.; Fei, M.; Zhang, H.; Santoro, J.; Wang, D. 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data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001.png" alt="Nanomaterials 14 01877 g001" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f001"></a> </div> </div> <div class="html-fig_description"> <b>Figure 1.</b> The utilization of syngas.  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f001"> <div class="html-caption"> <b>Figure 1.</b> The utilization of syngas.</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001.png" alt="Nanomaterials 14 01877 g001" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g001.png" /></div> </div> <div class="html-fig-wrap" id="nanomaterials-14-01877-f002"> <div class='html-fig_img'> <div class="html-figpopup html-figpopup-link" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f002"> <img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g002.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g002.png" alt="Nanomaterials 14 01877 g002" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g002-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f002"></a> </div> </div> <div class="html-fig_description"> <b>Figure 2.</b> TEM of nanoparticle (Ni).  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f002"> <div class="html-caption"> <b>Figure 2.</b> TEM of nanoparticle (Ni).</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g002.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g002.png" alt="Nanomaterials 14 01877 g002" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g002.png" /></div> </div> <div class="html-fig-wrap" id="nanomaterials-14-01877-f003"> <div class='html-fig_img'> <div class="html-figpopup html-figpopup-link" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f003"> <img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g003.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g003.png" alt="Nanomaterials 14 01877 g003" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g003-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f003"></a> </div> </div> <div class="html-fig_description"> <b>Figure 3.</b> Effect of pretreatment temperature and temperature on catalyst performance (Ni@SiO<sub>2</sub>) ((<b>a</b>): CH<sub>4</sub> of conversion, (<b>b</b>): CO<sub>2</sub> of conversion, (<b>c</b>): ration of H<sub>2</sub> and CO, (<b>d</b>): effect of reaction temperature).  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f003"> <div class="html-caption"> <b>Figure 3.</b> Effect of pretreatment temperature and temperature on catalyst performance (Ni@SiO<sub>2</sub>) ((<b>a</b>): CH<sub>4</sub> of conversion, (<b>b</b>): CO<sub>2</sub> of conversion, (<b>c</b>): ration of H<sub>2</sub> and CO, (<b>d</b>): effect of reaction temperature).</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g003.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g003.png" alt="Nanomaterials 14 01877 g003" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g003.png" /></div> </div> <div class="html-fig-wrap" id="nanomaterials-14-01877-f004"> <div class='html-fig_img'> <div class="html-figpopup html-figpopup-link" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f004"> <img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004.png" alt="Nanomaterials 14 01877 g004" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f004"></a> </div> </div> <div class="html-fig_description"> <b>Figure 4.</b> Effects of core and shell of catalysts on carbon deposit.  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f004"> <div class="html-caption"> <b>Figure 4.</b> Effects of core and shell of catalysts on carbon deposit.</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004.png" alt="Nanomaterials 14 01877 g004" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g004.png" /></div> </div> <div class="html-fig-wrap" id="nanomaterials-14-01877-f005"> <div class='html-fig_img'> <div class="html-figpopup html-figpopup-link" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f005"> <img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005.png" alt="Nanomaterials 14 01877 g005" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f005"></a> </div> </div> <div class="html-fig_description"> <b>Figure 5.</b> X-ray diffractograms of four reduced catalysts.  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f005"> <div class="html-caption"> <b>Figure 5.</b> X-ray diffractograms of four reduced catalysts.</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005.png" alt="Nanomaterials 14 01877 g005" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g005.png" /></div> </div> <div class="html-fig-wrap" id="nanomaterials-14-01877-f006"> <div class='html-fig_img'> <div class="html-figpopup html-figpopup-link" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f006"> <img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006.png" alt="Nanomaterials 14 01877 g006" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f006"></a> </div> </div> <div class="html-fig_description"> <b>Figure 6.</b> TGA of spent catalysts (Ni@SiO<sub>2</sub>, Ni(M)@SiO<sub>2</sub>, Ni@CeO<sub>2</sub>, and Ni(M)@CeO<sub>2</sub>).  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f006"> <div class="html-caption"> <b>Figure 6.</b> TGA of spent catalysts (Ni@SiO<sub>2</sub>, Ni(M)@SiO<sub>2</sub>, Ni@CeO<sub>2</sub>, and Ni(M)@CeO<sub>2</sub>).</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006.png" alt="Nanomaterials 14 01877 g006" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g006.png" /></div> </div> <div class="html-fig-wrap" id="nanomaterials-14-01877-f007"> <div class='html-fig_img'> <div class="html-figpopup html-figpopup-link" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f007"> <img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007.png" alt="Nanomaterials 14 01877 g007" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007-550.jpg" /> <a class="html-expand html-figpopup" data-counterslinkmanual = "https://www.mdpi.com/2079-4991/14/23/1877/display" href="#fig_body_display_nanomaterials-14-01877-f007"></a> </div> </div> <div class="html-fig_description"> <b>Figure 7.</b> Ni 2p and Ce 3d XPS spectra of spent Ni@CeO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> catalysts. ((<b>A</b>): Ni 2p, (<b>B</b>): Ce 3d).  </div> </div> <div class="html-fig_show mfp-hide" id="fig_body_display_nanomaterials-14-01877-f007"> <div class="html-caption"> <b>Figure 7.</b> Ni 2p and Ce 3d XPS spectra of spent Ni@CeO<sub>2</sub> and Ni(M)@CeO<sub>2</sub> catalysts. ((<b>A</b>): Ni 2p, (<b>B</b>): Ce 3d).</div> <div class="html-img"><img data-large="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007.png" data-original="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007.png" alt="Nanomaterials 14 01877 g007" data-lsrc="/nanomaterials/nanomaterials-14-01877/article_deploy/html/images/nanomaterials-14-01877-g007.png" /></div> </div> </section><section class='html-fn_group'><table><tr id=''><td></td><td><div class='html-p'><b>Disclaimer/Publisher’s Note:</b> The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). 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Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO<sub>2</sub> and CeO<sub>2</sub>). <em>Nanomaterials</em> <b>2024</b>, <em>14</em>, 1877. https://doi.org/10.3390/nano14231877 </p> <div style="display: block"> <b>AMA Style</b><br> <p> Hua D, Li J, Guo X, Lu X, Ding H, He R. Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO<sub>2</sub> and CeO<sub>2</sub>). <em>Nanomaterials</em>. 2024; 14(23):1877. https://doi.org/10.3390/nano14231877 </p> <b>Chicago/Turabian Style</b><br> <p> Hua, Derun, Jian Li, Xiaowen Guo, Xinning Lu, Hao Ding, and Rengui He. 2024. "Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO<sub>2</sub> and CeO<sub>2</sub>)" <em>Nanomaterials</em> 14, no. 23: 1877. https://doi.org/10.3390/nano14231877 </p> <b>APA Style</b><br> <p> Hua, D., Li, J., Guo, X., Lu, X., Ding, H., & He, R. (2024). Syngas from Reforming Methane and Carbon Dioxide on Ni@M(SiO<sub>2</sub> and CeO<sub>2</sub>). <em>Nanomaterials</em>, <em>14</em>(23), 1877. https://doi.org/10.3390/nano14231877 </p> </div> </div> <div class="info-box no-margin"> Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. 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