{"id":134809,"date":"2018-04-16T06:30:09","date_gmt":"2018-04-15T22:30:09","guid":{"rendered":"\/\/m.iemloyee.com\/?p=134809"},"modified":"2018-04-16T01:49:11","modified_gmt":"2018-04-15T17:49:11","slug":"jacs%ef%bc%9a%e5%85%89%e8%af%b1%e5%af%bcmof%e9%85%8d%e4%bd%93%e5%90%91ru2%e6%ac%a1%e7%ba%a7%e6%9e%84%e5%bb%ba%e5%8d%95%e5%85%83%e6%b3%a8%e5%b0%84%e7%94%b5%e5%ad%90%e5%ae%9e%e7%8e%b0%e5%8f%af%e8%a7%81","status":"publish","type":"post","link":"\/\/m.iemloyee.com\/?p=134809","title":{"rendered":"JACS\uff1a\u5149\u8bf1\u5bfcMOF\u914d\u4f53\u5411Ru2\u6b21\u7ea7\u6784\u5efa\u5355\u5143\u6ce8\u5c04\u7535\u5b50\u5b9e\u73b0\u53ef\u89c1\u5149\u9a71\u52a8\u6790\u6c22"},"content":{"rendered":"

\u3010\u5f15\u8a00\u3011<\/strong><\/p>\n

\u91d1\u5c5e-\u6709\u673a\u9aa8\u67b6\u7ed3\u6784\uff08MOFs\uff09\u4e3a\u63a2\u7a76\u4eba\u5de5\u5149\u5408\u4f5c\u7528\u7684\u5173\u952e\u6b65\u9aa4\u63d0\u4f9b\u4e86\u4e00\u4e2a\u591a\u529f\u80fd\u7684\u6750\u6599\u5e73\u53f0\u3002\u535f\u5549\u4f5c\u4e3a\u5149\u654f\u5242\uff0cRu2<\/sub>\u6b21\u7ea7\u6784\u5efa\u5355\u5143\uff08Ru2<\/sub> SBUs\uff09\u4f5c\u4e3a\u50ac\u5316\u4e2d\u5fc3\uff0c\u540c\u65f6\u5229\u7528\u5408\u6210\u53ef\u8c03\u6027\u548c\u7ed3\u6784\u89c4\u5f8b\u6027\u8bbe\u8ba1MOF\u591a\u5b54\u7ed3\u6784\uff08Ru-TBP\uff09\uff0c\u5b9e\u73b0\u4eba\u5de5\u5149\u5408\u4f5c\u7528\u3002\u5149\u50ac\u5316\u6790\u6c22\u53cd\u5e94\uff08HER\uff09\u662f\u4eba\u5de5\u5149\u5408\u4f5c\u7528\u7684\u4e00\u4e2a\u91cd\u8981\u5206\u652f\u3002\u5728HER\u6d4b\u8bd5\u8fc7\u7a0b\u4e2d\uff0cMOFs\u4e2d\u8d77\u5149\u6fc0\u53d1\u6216\u5149\u6291\u5236\u4f5c\u7528\u7684\u5149\u654f\u5242\u80fd\u591f\u6709\u6548\u5730\u5c06\u591a\u7535\u5b50\u6ce8\u5165\u5230\u76f8\u90bb\u7684\u50ac\u5316\u4e2d\u5fc3\uff0c\u4f7f\u5f97\u8d28\u5b50\u5f97\u5230\u7535\u5b50\u88ab\u8fd8\u539f\uff0c\u4ece\u800c\u4ea7\u751f\u6c22\u6c14\u3002\u672c\u6587\u7684\u521b\u65b0\u70b9\u5728\u4e8e\u57fa\u4e8eRu2<\/sub> SBUs\u548c\u535f\u5549\u884d\u751f\u7684\u56db\u7fa7\u57fa\u914d\u4f53\uff0c\u8bbe\u8ba1\u51fa\u4e24\u79cd\u65b0\u578b\u7684MOFs\u7ed3\u6784\uff0cRu-TBP\u548cRu-TBP-Zn\uff0c\u5176HER\u6d3b\u6027\u662f\u5747\u76f8\u5bf9\u7167\u7ed3\u679c\u768428\u500d\u3002<\/p>\n

\u3010\u6210\u679c\u7b80\u4ecb\u3011<\/strong><\/p>\n

\u8fd1\u65e5\uff0c\u7f8e\u56fd\u829d\u52a0\u54e5\u5927\u5b66\u6797\u6587\u658c\u6559\u6388\uff08\u901a\u8baf\u4f5c\u8005\uff09<\/strong>\u5728\u671f\u520aJACS<\/strong>\u4e0a\u4ee5\u9898\u4e3aElectron Injection from Photoexcited Metal\u2013Organic Framework Ligands to Ru2<\/sub> Secondary Building Units for Visible-Light-Driven Hydrogen Evolution<\/strong>\u53d1\u8868\u4e00\u7bc7\u6587\u7ae0\u3002\u8be5\u6587\u7ae0\u9996\u6b21\u63d0\u51fa\u4ee5\u535f\u5549\u4f5c\u4e3a\u5149\u654f\u5242\uff0c Ru2<\/sub> SBUs\u4f5c\u4e3a\u50ac\u5316\u4e2d\u5fc3\u5408\u6210\u4e24\u79cd\u65b0\u578bMOFs\u7ed3\u6784\uff08Ru-TBP \u548c Ru-TBP-Zn\uff09\u3002\u540c\u65f6\u7814\u7a76\u8005\u53d1\u73b0Ru-TBP \u548c Ru-TBP-Zn\u5177\u6709\u6781\u5f3a\u7684HER\u6d3b\u6027\uff0c\u5e76\u901a\u8fc7\u5149\u7269\u7406\u548c\u7535\u5316\u5b66\u7814\u7a76\uff0c\u63ed\u793a\u4e86Ru2<\/sub> SBUs\u662fHER\u8fc7\u7a0b\u4e2d\u7684\u5173\u952e\u6b65\u9aa4\u4ee5\u53ca\u50ac\u5316\u5faa\u73af\u4e2d\u95f4\u4f53\u7684\u80fd\u91cf\u67a2\u7ebd\uff0c\u5bf9\u6fc0\u53d1\u6001\u535f\u5549\u5177\u6709\u6c27\u5316\u6b82\u706d\u4f5c\u7528\u3002\u672c\u6587\u6210\u679c\u4e3a\u6784\u5efa\u591a\u529f\u80fdMOFs\u4ee5\u5b9e\u73b0\u9ad8\u6548\u5149\u50ac\u5316\u63d0\u4f9b\u4e86\u65b0\u7684\u601d\u8def\u3002<\/p>\n

\u3010\u56fe\u6587\u5bfc\u8bfb\u3011<\/strong><\/p>\n

\u56fe\u4e00 <\/strong>Ru-TBP\u6676\u4f53\u7ed3\u6784\u53ca\u5176HER\u53cd\u5e94\u673a\u7406\u793a\u610f\u56fe<\/p>\n

\"\"<\/p>\n

(a) Ru-TBP\u6676\u4f53\u7ed3\u6784\u5728\uff08100\uff09\u65b9\u5411\u7684\u900f\u89c6\u56fe\u3002\u76f8\u90bb\u535f\u5549\u4e2d\u5fc3\u548cRu2<\/sub> SBUs\u95f4\u8ddd\u4e3a\uff5e1.1 nm\uff0c\u800c\u76f8\u90bbRu2<\/sub> SBUs\u95f4\u8ddd\u4e3a\uff5e1.6 nm\uff1b<\/p>\n

(b) Ru2<\/sub> SBUs\u7684\u914d\u4f4d\u73af\u5883\uff1b<\/p>\n

(c) Ru-TBP\u6216Ru-TBP-Zn\u7684\u53ef\u89c1\u5149\u9a71\u52a8\u50ac\u5316HER\u793a\u610f\u56fe\u3002\u5149\u81f4\u535f\u5549\u914d\u4f53\u5c06\u7535\u5b50\u6ce8\u5165\u76f8\u90bbRu2<\/sub> SBUs\u4ee5\u8fd8\u539f\u8d28\u5b50\u6c22\u3002\u901a\u8fc7\u727a\u7272\u4e09\u4e59\u9187\u80fa\u8fd8\u539f\u6c27\u5316\u7684\u535f\u5549\u914d\u4f53\u4ee5\u518d\u751f\u5149\u50ac\u5316\u7cfb\u7edf\u3002<\/p>\n

\u56fe\u4e8c <\/strong>Ru-TBP\u53caRu-TBP-Zn\u7684\u51e0\u79cd\u5fae\u89c2\u8868\u5f81<\/p>\n

\"\"<\/p>\n

(a) Ru-TBP\u7684TEM\u56fe\uff1b<\/p>\n

(b) Ru-TBP\u7684HRTEM\u56fe\u548cFFT\u56fe\uff08\u63d2\u56fe\uff09\uff1b<\/p>\n

(c) Ru-TBP-Zn\u7684TEM\u56fe\uff1b<\/p>\n

(d) Ru-TBP-Zn\u7684HRTEM\u56fe\u548cFFT\u56fe\uff08\u63d2\u56fe\uff09\uff1b<\/p>\n

(e) Ru-TBP\u548cRu-TBP-Zn\u7684PXRD\u56fe\uff1b<\/p>\n

(f) Ru-TBP\u548cRu-TBP-Zn\u7684\u6c2e\u5438\u9644\u7b49\u6e29\u7ebf\uff1b<\/p>\n

(g) Ru-TBP\u548cRu-TBP-Zn\u7684Ru 3p XPS\u8c31\u56fe\uff1b<\/p>\n

(h) Ru-TBP\u548cRu-TBP-Zn\u7684\u7d2b\u5916\u53ef\u89c1\u5149\u5438\u6536\u8c31\u56fe\u3002<\/p>\n

\u56fe\u4e09 <\/strong>Ru-TBP\uff0cRu-TBP-Zn\u548cRu2-PD + H4TBP-Zn\u7684TONs\u968f\u65f6\u95f4\u53d8\u5316\u8d8b\u52bf\u53ca\u5176\u53cd\u5e94\u524d\u540e\u7ec4\u5206\u7684\u53d8\u5316<\/p>\n

\"\"<\/p>\n

(a) Ru-TBP\uff0cRu-TBP-Zn\u548c\u5747\u76f8\u5bf9\u7167\u7684HERTONs-\u65f6\u95f4\u56fe\uff08N=3\uff09\uff1b<\/p>\n

(b) Ru-TBP\u548cRu-TBP-Zn\u5149\u50ac\u5316\u524d\u540e\u7684PXRD\u56fe\u3002<\/p>\n

\u56fe\u56db <\/strong>Ru-TBP-Zn\u548cRu2-PD + Me4TBP-Zn\u901a\u8fc7\u5149\u7269\u7406\u548c\u7535\u5316\u5b66\u6d4b\u8bd5\u7814\u7a76HER\u673a\u7406<\/p>\n

\"\"<\/p>\n

(a)\u57282 mL CH3<\/sub>CN\u548c410 nm\u5149\u6fc0\u53d1\u4e0b\uff0c\u4e0d\u540c Ru2<\/sub>-PD\u6dfb\u52a0\u91cf\u4e0bMe4<\/sub>TBP-Zn\uff080.1 mg\/mL\uff09\u7684\u53d1\u5c04\u5149\u8c31\u56fe\uff1b<\/p>\n

(b) \u57282 mL CH3<\/sub>CN\u548c410 nm\u5149\u6fc0\u53d1\u4e0b\uff0c\u4e0d\u540c TEOA\u6dfb\u52a0\u91cf\u4e0bMe4<\/sub>TBP-Zn\uff080.1 mg\/mL\uff09\u7684\u53d1\u5c04\u5149\u8c31\u56fe\uff1b<\/p>\n

(c) \u4f5c\u4e3aRu2<\/sub>-PD\u6d53\u5ea6\u7684\u51fd\u6570\u7684IO<\/sub>\/I\u56fe\uff1b<\/p>\n

(d) \u5728\u542b\u670920 mL 0.1 M TBAH\/CH3<\/sub>CN\uff0c500 \u03bcL\u6c34\u548c500 \u03bcL TFA\u7684\u6eb6\u6db2\u4e2d\uff0c5 mM Ru2<\/sub>-PD\u548c0.5 mg Ru-TBP-Zn\u6d82\u8986\u5728\u7535\u6781\u8868\u9762\u7684CV\u56fe\uff08TBAH=\u56db\u4e01\u57fa\u6c22\u6c27\u5316\u94f5\uff09\uff1b<\/p>\n

(e) Ru-TBP-Zn\u7684\u53ef\u89c1\u5149\u9a71\u52a8\u50ac\u5316\u6790\u6c22\u7684\u5faa\u73af\u56fe\uff0c\u2206E1<\/sub> = 2.05 eV\uff0c\u2206E2<\/sub> = -1.12 eV\uff0c\u2206E3<\/sub> = -0.93 eV\uff0c\u2206E\u2019 = 0.93 eV\u3002<\/p>\n

\u3010\u5c0f\u7ed3\u3011<\/strong><\/p>\n

\u672c\u6587\u5408\u6210\u4e86\u4e24\u79cd\u65b0\u578bMOFs\u7ed3\u6784\uff1aRu-TBP\u548cRu-TBP-Zn\uff0c\u5b9e\u73b0\u5c06HER\u50ac\u5316\u5242\uff08\u5982\u535f\u5549\u884d\u751f\u7684\u56db\u7fa7\u57fa\u914d\u4f53\uff09\u76f4\u63a5\u5e76\u5165\u5149\u654fMOFs\u6750\u6599\uff08\u5982Ru2<\/sub> SBUs\uff09\u4e2d\u5b8c\u6210\u5149\u50ac\u5316HER\u3002Ru2<\/sub> SBUs\u540c\u5149\u654f\u535f\u5549\u914d\u4f53\u76f8\u8ddd\u4ec5\uff5e1.1 nm\uff0c\u4e3a\u7535\u5b50\u4ece\u535f\u5549\u914d\u4f53\u8f6c\u79fb\u81f3Ru2<\/sub> SBUs\u63d0\u4f9b\u53ef\u80fd\u3002Ru-TBP \u548c Ru-TBP-Zn\u662fHER\u9ad8\u6d3b\u6027\u6750\u6599\uff0c\u5176TONs\u8fdc\u9ad8\u4e8e\u5747\u76f8\u5bf9\u7167\u5b9e\u9a8c\u3002\u5728\u5149\u7269\u7406\u548c\u7535\u5316\u5b66\u7684\u7814\u7a76\u4e2d\uff0cRu2<\/sub> SBUs\u663e\u793a\u51fa\u5bf9 (TBP-Zn)* \u6fc0\u53d1\u6001\u7684\u6709\u6c27\u5316\u6b82\u706d\u4f5c\u7528\uff0c\u540c\u65f6\u8fd8\u662f\u50ac\u5316\u5faa\u73af\u4e2d\u95f4\u4f53\u7684\u80fd\u91cf\u67a2\u7ebd\u3002\u672c\u6587\u7684\u7814\u7a76\u4e3a\u5408\u6210\u5177\u6709\u9ad8\u6548\u5149\u50ac\u5316\u6548\u5e94\u7684\u65b0\u578bMOFs\u6750\u6599\u63d0\u4f9b\u4e86\u65b0\u7684\u601d\u8def\u3002<\/p>\n

\u6587\u732e\u94fe\u63a5\uff1a<\/strong>Electron Injection from Photoexcited Metal\u2013Organic Framework Ligands to Ru2<\/sub> Secondary Building Units for Visible-Light-Driven Hydrogen Evolution<\/a>\uff08<\/strong>J. Am. Chem. Soc., 2018, DOI: 10.1021\/jacs.8b01601\uff09<\/p>\n

\u672c\u6587\u7531\u6750\u6599\u4eba\u7f16\u8f91\u90e8\u65b0\u4eba\u7ec4\u77f3\u7f57\u7433\u7f16\u8f91\uff0c\u8d75\u98de\u9f99\u5ba1\u6838\uff0c\u70b9\u6211\u52a0\u5165\u6750\u6599\u4eba\u7f16\u8f91\u90e8<\/a>\u3002<\/p>\n

\u6750\u6599\u6d4b\u8bd5\u3001\u6570\u636e\u5206\u6790\uff0c\u4e0a<\/strong>\u6d4b\u8bd5\u8c37<\/strong><\/a>\uff01<\/strong><\/p>\n","protected":false},"excerpt":{"rendered":"

\u3010\u5f15\u8a00\u3011 \u91d1\u5c5e-\u6709\u673a\u9aa8\u67b6\u7ed3\u6784\uff08MOFs\uff09\u4e3a\u63a2\u7a76\u4eba\u5de5\u5149\u5408\u4f5c\u7528\u7684\u5173\u952e\u6b65\u9aa4\u63d0\u4f9b\u4e86\u4e00\u4e2a\u591a\u529f\u80fd\u7684\u6750\u6599\u5e73\u53f0\u3002\u535f\u5549\u4f5c\u4e3a\u5149\u654f\u5242\uff0cRu2\u6b21\u7ea7\u6784\u5efa\u5355\u5143\uff08Ru2 SBUs\uff09\u4f5c\u4e3a\u50ac\u5316\u4e2d…<\/p>\n","protected":false},"author":230,"featured_media":134812,"comment_status":"open","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[215,2],"tags":[3064],"class_list":["post-134809","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-jiedu","category-keji","tag-her"],"_links":{"self":[{"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/posts\/134809"}],"collection":[{"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/users\/230"}],"replies":[{"embeddable":true,"href":"\/\/m.iemloyee.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=134809"}],"version-history":[{"count":5,"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/posts\/134809\/revisions"}],"predecessor-version":[{"id":135219,"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/posts\/134809\/revisions\/135219"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/m.iemloyee.com\/index.php?rest_route=\/wp\/v2\/media\/134812"}],"wp:attachment":[{"href":"\/\/m.iemloyee.com\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=134809"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/m.iemloyee.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=134809"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/m.iemloyee.com\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=134809"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}