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'北京大学李星国 J Mater Chem A：等离子体与MOF的“碰撞”制备高分散性析氢催化剂'

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'【引言】金属有机骨架材料（Metal organic frameworks，MOFs） 是是由金属离子和有机配体组装而成的新型三维多孔材料，其规整性及多样性等特性为设计各种需求的催化剂提供了一个理想的'

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'<p><strong><img alt="" src="https://img.ruilang.cn/psmplasma.com/uploadfile/201908/f2b6edfc5ab77bc.jpg" style="width: 278px; height: 208px;" /><br />
【引言】</strong></p>

<p>金属有机骨架材料（Metal organic frameworks，MOFs）&nbsp;是是由金属离子和有机配体组装而成的新型三维多孔材料，其规整性及多样性等特性为设计各种需求的催化剂提供了一个理想的平台。通过高温热处理是去除MOFs中配体部分将其转化为相关衍生材料（氧化物，碳包覆金属等）的是目前制备纳米催化材料的一种有效策略，至今，以&nbsp;MOFs&nbsp;为前驱体/牺牲模板，已经成功制备了大量具有复杂组成、结构和功能的纳米结构催化剂。</p>

<p>然而，大多数工作的热转化条件往往需要非常高的温度（600 ~900 ℃），这样的高温热处理过程不仅比较耗能，而且热解过程中金属原子极易发生团聚，导致催化剂颗粒变大，其中的活性位点的密度因金属的团聚而减小，阻碍了反应物与部分活性位点的接触，无法充分发挥材料的催化活性。</p>

<p>&nbsp;</p>

<p>【成果简介】</p>

<p>基于此，近日，<strong>北京大学李星国教授和郑捷副教授课题组发展了一种新型的氨气气氛下低温等离子体对</strong><strong>MOFs</strong><strong>材料的改性策略，将具有高化学活性的&nbsp;NH<sub>3</sub>&nbsp;plasma</strong><strong>引入对Ni</strong><strong>基MOF</strong><strong>的处理过程中，得到氮掺杂寡层碳包覆的超微镍纳米颗粒（Ni@NC</strong><strong>）作为高性能氢析出反应（HER</strong><strong>）催化剂，并对NH<sub>3</sub>&nbsp;plasma</strong><strong>与MOFs</strong><strong>材料的相互作用机制进行了研究。</strong></p>

<p><strong>&nbsp;</strong></p>

<p>NH<sub>3</sub>等离子体的引入既可通过化学刻蚀作用降低大大降低&nbsp;MOFs的分解温度，同时等离子体中的含氮活性物种（Reactive nitrogen species, RNS）可促进配体的快速碳化，极大地抑制了纳米颗粒的迁移和团聚现象，得到具有“杨桃型”特征形貌的超微&nbsp;Ni&nbsp;纳米颗粒（2~3 nm），使金属位点充分暴露，提高纳米结构的催化活性，在&nbsp;10 mA cm<sup>-2</sup>&nbsp;电流密度下HER过电势仅为&nbsp;61 mV。同时，该&nbsp;Ni@NC&nbsp;催化剂可应用于微型的太阳能-氢能能量转换系统中，成功在大电流密度下持续产生氢气，有望实现以太阳能为能量来源耦合电解水技术持续产氢的实际应用。<strong>相关成果以题为“Plasma modification of a Ni based metal&ndash;organic framework forefficient hydrogen evolution”的文章发表于J. Mater. Chem. A上，第一作者为北京大学郭妍如博士。</strong></p>

<p>&nbsp;</p>

<p><strong>【图文导读】</strong></p>

<p><img alt="" src="https://img.ruilang.cn/psmplasma.com/uploadfile/201908/c1f2f705b4c1760.jpg" style="width: 278px; height: 208px;" /></p>

<p>图1 &nbsp;a) NH<sub>3</sub>气氛等离子体与NH<sub>3</sub>气氛直接热解处理Ni MOF-74示意图；不同样品的SEM图：b）Ni MOF-74，c~d) NH<sub>3</sub>-plasma样品，e~f）NH<sub>3</sub>-thermal样品，g）Ar-plasma样品</p>

<p>&nbsp;</p>

<p><img alt="" src="https://img.ruilang.cn/psmplasma.com/uploadfile/201908/c4eac925b17d2c9.jpg" style="width: 278px; height: 208px;" /></p>

<p>图2&nbsp;样品的TEM和HRTEM图：a, d, e) NH<sub>3</sub>-plasma样品，b）NH<sub>3</sub>-thermal样品，c, f）Ar-plasma样品</p>

<p>&nbsp;</p>

<p><img alt="" src="https://img.ruilang.cn/psmplasma.com/uploadfile/201908/dd6347d715491cb.jpg" style="width: 278px; height: 208px;" /></p>

<p>图3 &nbsp;a）前驱体Ni MOF-74的XRD图；b~d）不同条件处理样品的表征：b）XRD图，c）Raman图谱；d）N 1s图谱</p>

<p>&nbsp;</p>

<p><img alt="" src="https://img.ruilang.cn/psmplasma.com/uploadfile/201908/bc994868bf9a.jpg" style="width: 278px; height: 208px;" /></p>

<p>图4&nbsp;样品电化学性能测试：a）LSV曲线；b）Tafel斜率；c）法拉第效率；d）与商用Si太阳能电池联用的两电极全电解性能（NH<sub>3</sub>-plasma样品为HER催化剂，光强：AM1.5，100 mW cm<sup>-2</sup>）；e）全电解测试稳定性；f）稳定性测试后样品TEM图；g）微型的太阳能-氢能能量转换系统实物照片；h）系统能量损失图</p>

<p>&nbsp;</p>

<p><strong>【小结】</strong></p>

<p>等离子体技术作为一项集物理学、化学、生物学和环境科学于一体的交叉综合性技术，近些年来在材料制备和改性方面产生了很多新兴应用研究，如对材料进行表面处理、掺杂、缺陷制造等，该研究工作将等离子体与对金属有机骨架的改性联系起来，碰撞出新的火花，为MOFs材料的修饰和应用开辟了新的思路。同时，高度化学反应性和低热效应的组合使得低温等离子体有望成为开发高性能催化剂的非常有前途的技术。</p>

<p>&nbsp;</p>

<p>&nbsp;</p>

<p>Guo, Y.; Gao, X.; Zhang, C.; Wu, Y.;Chang, X.; Wang, T.; Zheng, X.; Du, A.; Wang, B.; Zheng, J.; Ostrikov, K.; Li,X. Plasma modification of a Ni based metal&ndash;organic framework for efficienthydrogen evolution.&nbsp;<em>Journal of Materials Chemistry A.&nbsp;</em>2019, 7, 8129-8135.</p>

<p>DOI:10.1039/C9TA00696F</p>
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  'nText' => '<h2 style="font-weight:bold;font-size:28px;">普仕曼科技</h2><p style="font-size:14px">专注等离子体表面处理设备</p><p>&nbsp;</p><p style="font-size:18px">质量为根本<br/>市场为导向<br/>人才为核心</p>',
  'M2' => '23',
  'M3' => '31',
  'ditubiaozhu' => '113.811818,22.717887',
  'tianditukey' => '55f4dc93d4b791534be8342cbe7440ca ',
)

array (
  'company' => '公司名称',
  'contact' => '联系人',
  'telephone' => '联系电话',
  'mobile' => '手机',
  'email' => '邮箱',
  'erweima' => '二维码',
  'postcode' => '邮编',
  'address' => '联系地址',
  'T1' => '产品',
  'T2' => '应用',
  'T3' => '关于',
  'T4' => '新闻',
  'T5' => '伙伴',
  'T7' => '内页默认导航',
  'nText' => '内页右侧富文本',
  'M2' => '手机导航1',
  'M3' => '手机导航2',
  'ditubiaozhu' => '地图标注',
  'tianditukey' => '天地图key',
)