{"id":36344,"date":"2020-12-21T08:00:05","date_gmt":"2020-12-21T00:00:05","guid":{"rendered":"\/\/www.gsbet888.com\/?p=36344"},"modified":"2020-12-16T22:15:12","modified_gmt":"2020-12-16T14:15:12","slug":"%e5%8f%af%e8%a7%81%e5%85%89%e4%bf%83%e8%bf%9b%e9%9d%9e%e9%87%91%e5%b1%9e%e5%82%ac%e5%8c%96%e7%9a%84%e4%bb%8ecsp3-h%e9%94%ae%e5%90%88%e6%88%90%e8%8a%b3%e8%85%88%e5%8c%96%e5%90%88%e7%89%a9","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2020\/12\/%e5%8f%af%e8%a7%81%e5%85%89%e4%bf%83%e8%bf%9b%e9%9d%9e%e9%87%91%e5%b1%9e%e5%82%ac%e5%8c%96%e7%9a%84%e4%bb%8ecsp3-h%e9%94%ae%e5%90%88%e6%88%90%e8%8a%b3%e8%85%88%e5%8c%96%e5%90%88%e7%89%a9.html","title":{"rendered":"\u53ef\u89c1\u5149\u4fc3\u8fdb\u975e\u91d1\u5c5e\u50ac\u5316\u7684\u4eceC(sp3)-H\u952e\u5408\u6210\u82b3\u8148\u5316\u5408\u7269"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005\uff1aChemBoy<\/strong><\/p>\n

\u5bfc\u8bfb<\/h4>\n

\u5728\u6709\u673a\u5408\u6210\u4e2d\uff0cC(sp3)-H\u952e\u5728\u975e\u91d1\u5c5e\u6d3b\u5316\u4f5c\u7528\u4e0b\u8f6c\u5316\u6210\u9ad8\u9644\u52a0\u503c\u5316\u5408\u7269\u662f\u4e00\u4e2a\u975e\u5e38\u91cd\u8981\u7684\u7814\u7a76\u9886\u57df\u3002\u6700\u8fd1\uff0c\u5fb7\u56fd\u96f7\u6839\u65af\u5821\u5927\u5b66Burkhard K\u00f6nig\u6559\u6388\u8bfe\u9898\u7ec4\u5229\u7528\u5546\u4e1a\u53ef\u5f97\u7684\u6709\u673a\u67d3\u65992,4,6-\u4e09\u82ef\u57fa\u5421\u5576\u56db\u6c1f\u787c\u9178\u76d0\uff08TPP\uff09\u4f5c\u4e3a\u5149\u654f\u5242\uff0c\u5728\u53ef\u89c1\u5149\u8f90\u5c04\u6761\u4ef6\u4e0b\u5b9e\u73b0\u4e86\u4eceC(sp3)-H\u952e\u8f6c\u5316\u6210\u6c30\u57fa\u7684\u65b9\u6cd5\uff0c\u901a\u8fc7\u8fd9\u79cd\u65b9\u6cd5\u53ef\u4ee5\u4ece\u7532\u57fa\uff08\u6742\uff09\u82b3\u70c3\u5408\u6210\u4e00\u7cfb\u5217\u7684\uff08\u6742\uff09\u82b3\u8148\u5316\u5408\u7269\u3002\u4ed6\u4eec\u7684\u65b9\u6cd5\u907f\u514d\u4e86\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u548c\u6709\u6bd2\u6c30\u5316\u7269\u7684\u4f7f\u7528\uff0c\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u5728\u300aAngew. Chem. Int. Ed.\u300b\u4e0a\uff1a<\/p>\n

\u201cVisible-Light-Promoted Metal-Free Synthesis of (Hetero)aromatic Nitriles from C(sp3)-H bonds\u201d
\nKathiravan Murugesan, Karsten Donabauer, and Burkhard K\u00f6nig*
\nAngew. Chem. Int. Ed. 2020, Accepted Articles, 10.1002\/anie.202011815\u00a0https:\/\/doi.org\/10.1002\/anie.202011815<\/a><\/p><\/blockquote>\n

\"\"<\/a><\/p>\n

\u6b63\u6587<\/h4>\n

\u524d\u8a00<\/span><\/strong>
\n\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u5728\u4e00\u4e9b\u5de5\u4e1a\u751f\u4ea7\u3001\u7cbe\u7ec6\u5316\u5b66\u54c1\u548c\u5927\u5b97\u5316\u5b66\u54c1\u7684\u5408\u6210\u53cd\u5e94\u4e2d\u662f\u4e0d\u53ef\u6216\u7f3a\u7684\u3002\u5728\u8fc7\u53bb\u4e8c\u5341\u5e74\u91cc\uff0c\u4e00\u4e9b\u901a\u8fc7\u70ed\u5316\u5b66\u6216\u5149\u5316\u5b66\u9014\u5f84\u8fdb\u884c\u7684C(sp3<\/sup>)-H\u952e\u6d3b\u5316\u7684\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u5df2\u7ecf\u88ab\u53d1\u5c55\u3002\u5176\u4e2d\u4e00\u79cd\u91cd\u8981\u7684\u8f6c\u5316\u5c31\u662f\u5c06\u77f3\u6cb9\u5316\u5de5\u526f\u4ea7\u54c1\u8f6c\u5316\u6210\u7cbe\u7ec6\u5316\u5b66\u54c1\uff0c\u6bd4\u5982\u4ece\u7532\u82ef\u5408\u6210\u82ef\u8148\u7684\u8f6c\u5316\u3002\u5728\u5de5\u4e1a\u4e0a\uff0c\u82ef\u8148\u662f\u901a\u8fc7\u7532\u82ef\u5728\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\uff08\u9492\uff09\u4f5c\u7528\u4e0b\u3001\u6c28\u6c14\u548c\u6c27\u6c14\u9ad8\u538b\u9ad8\u6e29\uff08300-500 \u00baC\uff09\u6761\u4ef6\u4e0b\u53d1\u751f\u80fa\u6c27\u5316\u53cd\u5e94\u5236\u5907\u3002\u56e0\u4e3a\u6c30\u57fa\u4e0d\u4ec5\u662f\u5404\u79cd\u836f\u7269\u548c\u751f\u7269\u6d3b\u6027\u5206\u5b50\u4e2d\u7684\u5173\u952e\u5b98\u80fd\u56e2\u3001\u8fd8\u662f\u4e00\u4e9b\u7cbe\u7ec6\u548c\u5927\u5b97\u5316\u5b66\u54c1\u7684\u91cd\u8981\u5408\u6210\u780c\u5757\u3002\u6240\u4ee5\uff0c\u8fd1\u5e74\u6765\uff0c\u4e00\u4e9b\u65b0\u7684\u3001\u6761\u4ef6\u6e29\u548c\u7684\u3001\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\u4ece\u9187\u3001\u80fa\u3001\u919b\u6216\u662f\u7b80\u5355CH3<\/sub>\u5408\u6210\u6c30\u57fa\u5316\u5408\u7269\u7684\u53cd\u5e94\u65b9\u6cd5\u5df2\u7ecf\u88ab\u62a5\u9053[1]<\/sup>\u3002\u7136\u800c\uff0c\u5728\u8fd9\u4e9b\u65b9\u6cd5\u4e2d\uff0c\u5f88\u591a\u60c5\u51b5\u4e0b\u90fd\u9700\u8981\u5728\u8f83\u9ad8\u7684\u6e29\u5ea6\u4e0b\u53cd\u5e94\u3001\u751a\u81f3\u7ecf\u5e38\u9700\u8981\u4f7f\u7528\u9ad8\u6bd2\u6027\u7684\u6c30\u5316\u7269\u4f5c\u4e3a\u6c30\u57fa\u6e90\uff0c\u6216\u8005\u662f\u9700\u8981\u4f7f\u7528\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u3002\u9274\u4e8e\u8fd9\u4e9b\u65b9\u6cd5\u6240\u7528\u8bd5\u5242\u7684\u9ad8\u6210\u672c\u3001\u9ad8\u6bd2\u6027\u7b49\u7f3a\u70b9\uff0c\u53d1\u5c55\u65e0\u91d1\u5c5e\u50ac\u5316\u3001\u65e0\u6c30\u5316\u7269\u4f5c\u4e3a\u6c30\u57fa\u6e90\u3001\u5c24\u5176\u662f\u76f4\u63a5\u4eceC-H\u952e\u8f6c\u5316\u4e3a\u6c30\u57fa\u7684\u53cd\u5e94\u65b9\u6cd5\u662f\u975e\u5e38\u6709\u5fc5\u8981\u7684\u3002
\n\u8fd1\u5e74\u6765\uff0c\u51e0\u4f8b\u4f7f\u7528\u66f4\u7eff\u8272\u7684\u94f5\u76d0\u4f5c\u4e3a\u6c2e\u6e90\u3001\u901a\u8fc7\u5149\u5316\u5b66\u65b9\u6cd5\u5408\u6210\u8148\u7c7b\u5316\u5408\u7269\u7684\u53cd\u5e94\u5f97\u5230\u62a5\u9053\u3002\u5305\u62ec\u5229\u7528\u8fc7\u786b\u9178\u94f5\u4e3a\u6c2e\u6e90\u3001\u82b3\u919b\u5728\u948c\u5149\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u751f\u6210\u82b3\u8148\uff08Scheme 1A\uff09[2]<\/sup>\u6216\u8005\u662f\u82b3\u919b\u4e0e\u7f9f\u80fa\u76d0\u9178\u76d0\u5728\u591a\u76f8\u5149\u50ac\u5316\u5242Co@g-C3<\/sub>N4<\/sub>\u4f5c\u7528\u4e0b\u751f\u6210\u82b3\u8148\u7684\u53cd\u5e94\uff08Scheme 1B\uff09[3]<\/sup>\uff1b\u53e6\u5916\u4e00\u4f8b\u975e\u5e38\u6709\u610f\u601d\u7684\u53cd\u5e94\u662f\u82ef\u4e59\u70ef\u8f6c\u5316\u6210\u6c30\u57fa\u809f\u7684\u53cd\u5e94\uff08Scheme 1C\uff09[4]<\/sup>\u3002\u8fd9\u4e9b\u5149\u50ac\u5316\u5408\u6210\u6c30\u57fa\u7c7b\u5316\u5408\u7269\u7684\u53cd\u5e94\u90fd\u6210\u529f\u907f\u514d\u4e86\u9ad8\u6bd2\u6027\u6c30\u5316\u7269\u7684\u4f7f\u7528\u3002\u7136\u800c\uff0c\u7532\u57fa\u82b3\u70c3\u76f4\u63a5\u8f6c\u5316\u6210\u6c30\u57fa\u5316\u5408\u7269\u5bf9\u4e8e\u5de5\u4e1a\u7684\u6c28\u6c27\u5316\u53cd\u5e94\u6765\u8bf4\u662f\u66f4\u7b80\u5355\u6709\u6548\u5408\u6210\u8def\u5f84\u3002
\n\u57fa\u4e8e\u4ee5\u4e0a\u4e00\u4e9b\u56e0\u7d20\uff0c\u4f5c\u8005\u8bbe\u60f3\u662f\u5426\u53ef\u4ee5\u5229\u7528\u4e00\u79cd\u975e\u91d1\u5c5e\u5149\u50ac\u5316\u5242\u3001\u540c\u65f6\u65e0\u9700\u6c30\u5316\u7269\u4f5c\u4e3a\u6c30\u57fa\u6e90\uff0c\u76f4\u63a5\u5c06\u7532\u82ef\u4e00\u6b65\u8f6c\u5316\u4e3a\u82b3\u8148\u3002\u4f5c\u8005\u5047\u8bbe\uff0c\u7532\u57fa\u82b3\u70c3\uff08\u7532\u82ef\u7684\u6c27\u5316\u7535\u52bf\u4e3aE1\/2<\/sub> = +2.36 V vs.SCE\uff09\u53ef\u80fd\u4f1a\u88ab\u9ad8\u6c27\u5316\u6027\u7684\u5149\u50ac\u5316\u5242\u6d3b\u5316\u6216\u662f\u652b\u53d6\u82c4\u4f4d\u6c22\u539f\u5b50\u3002\u4f5c\u8005\u5728\u8fd9\u91cc\u5229\u7528\u4e00\u79cd\u5546\u4e1a\u53ef\u5f97\u7684\u6709\u673a\u67d3\u65992,4,6-\u4e09\u82ef\u57fa\u5421\u5576\u56db\u6c1f\u787c\u9178\u76d0\uff08TPP\uff09\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\u3001\u7f9f\u80fa\u76d0\u9178\u76d0\u4f5c\u4e3a\u80fa\u6e90\u3001\u6eb4\u5316\u94f5\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u5728\u6c27\u6c14\u6c1b\u56f4\u4e2d\u3001\u53ef\u89c1\u5149\u8f90\u5c04\u4e0b\u5b9e\u73b0\u4e86\u4ece\u7532\u82ef\u4e00\u6b65\u5408\u6210\u82b3\u8148\u7684\u53cd\u5e94\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u6761\u4ef6\u4f18\u5316<\/span><\/strong>
\n\u5728\u8fd9\u91cc\uff0c\u4f5c\u8005\u4ee54-\u7532\u57fa\u82ef\u7532\u9178\u7532\u916f1\u4f5c\u4e3a\u6a21\u677f\u5e95\u7269\u5bf9\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u4f18\u5316\uff08Table 1\uff09\u3002\u4f5c\u8005\u4ee5NH2<\/sub>OH\u2022HCl\u4f5c\u4e3a\u6c2e\u6e90\u3001NH4<\/sub>Br\u4f5c\u4e3a\u6dfb\u52a0\u5242\u3001\u6c27\u6c14\u4f5c\u4e3a\u6c27\u5316\u5242\u3001\u4e59\u8148\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u572840 \u00baC\u7684\u53cd\u5e94\u6e29\u5ea6\u3001\u6ce2\u957f\u4e3a455 nm\u7684\u53ef\u89c1\u5149\u7167\u5c04\u6761\u4ef6\u4e0b\uff0c\u5bf9\u4e00\u7cfb\u5217\u5546\u4e1a\u53ef\u5f97\u7684\u6709\u673a\u67d3\u6599\u8fdb\u884c\u4e86\u7b5b\u9009\u3002\u4f7f\u7528DDQ (PC-1)\u548c\u5416\u5576\u7c7b\u5149\u50ac\u5316\u5242\uff08PC-2\u3001PC-3\uff09\u65f6\uff0c\u5747\u80fd\u68c0\u6d4b\u5230\u76ee\u6807\u4ea7\u7269\uff0c\u4f46\u662f\u4ea7\u7387\u5f88\u4f4e\uff0812-26%\uff0cTable 1,entries 1-3\uff09\u3002\u4ee4\u4eba\u9ad8\u5174\u7684\u662f\uff0c\u5f53\u4f7f\u7528TPP(PC-4\uff0cE1\/2 = +2.55 V vs. SCE)\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\u65f6\u80fd\u4ee576%\u7684\u4ea7\u7387\u83b7\u5f97\u76ee\u6807\u4ea7\u72694-\u6c30\u57fa\u82ef\u7532\u9178\u7532\u916f2\uff08Table 1,entry 4\uff09\u3002\u4f5c\u8005\u8fd8\u5bf9\u5176\u4ed6\u6c2e\u6e90\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u5982\u4e59\u9178\u94f5\u548c\u6c28\u6c34\u5747\u6ca1\u6709\u68c0\u6d4b\u5230\u76ee\u6807\u4ea7\u7269\uff08Table 1,entry 5 and entry 6\uff09\uff0c\u4f5c\u8005\u8ba4\u4e3a\u8fd9\u79cd\u73b0\u8c61\u53ef\u80fd\u662f\u56e0\u4e3a\u8fd9\u79cd\u7b80\u5355\u94f5\u79bb\u5b50\u88ab\u6c27\u5316\u7684\u901f\u7387\u6bd4\u76ee\u6807\u5e95\u7269\u88ab\u6c27\u5316\u7684\u901f\u7387\u5feb\u4ee5\u53caPC-4\u5728\u78b1\u6216\u4eb2\u6838\u8bd5\u5242\u5b58\u5728\u6761\u4ef6\u4e0b\u4f1a\u5206\u89e3\u7b49\u539f\u56e0\u5bfc\u81f4\u7684\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u901a\u8fc7\u63a7\u5236\u5b9e\u9a8c\u53d1\u73b0\uff0c\u5149\u3001\u5149\u50ac\u5316\u5242\u3001\u6c27\u6c14\u548c\u7f9f\u80fa\u76d0\u9178\u76d0\u5bf9\u8be5\u53cd\u5e94\u7684\u987a\u5229\u8fdb\u884c\u81f3\u5173\u91cd\u8981\u3002
\n\u5728\u786e\u5b9a\u4e86\u5149\u50ac\u5316\u5242\u540e\uff0c\u4f5c\u8005\u8fd8\u5bf9\u53cd\u5e94\u6e29\u5ea6\u3001\u6eb4\u5316\u94f5\u548c\u7f9f\u80fa\u7684\u8d1f\u8f7d\u91cf\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\u8fdb\u884c\u4e86\u4ed4\u7ec6\u7684\u7814\u7a76\uff08Fig. 1\uff09\u3002\u5728\u4f4e\u6e29\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f1a\u6291\u5236\u526f\u4ea7\u7269\u809f3\u8131\u6c34\u751f\u6210\u76ee\u6807\u4ea7\u72692\uff08Fig.1a\uff09\uff1b\u6dfb\u52a0\u5242\u6eb4\u5316\u94f5\u7684\u5b58\u5728\u80fd\u591f\u6709\u6548\u4fc3\u8fdb\u53cd\u5e94\u7684\u8fdb\u884c\uff08Fig.1b\uff09;\u6b64\u5916\uff0c\u65e0\u5408\u9002\u7684\u6c2e\u6e90\u5b58\u5728\u6761\u4ef6\u4e0b\uff0c\u4f1a\u53d1\u751f\u8fc7\u5ea6\u6c27\u5316\u53cd\u5e94\u751f\u6210\u7fa7\u91784\uff08Fig.1c\uff09\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u809f3\u53ea\u6709\u5728\u5149\u50ac\u5316\u6761\u4ef6\u4e0b\u624d\u80fd\u8f6c\u5316\u751f\u6210\u76ee\u6807\u4ea7\u72692\uff08Fig.1d\uff09\u3002<\/p>\n

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\"\"<\/a><\/p>\n

\u673a\u7406\u5047\u8bbe<\/span><\/strong>
\n\u901a\u8fc7\u6761\u4ef6\u7b5b\u9009\uff0c\u4f5c\u8005\u53d1\u73b0\u809f3\u662f\u8be5\u53cd\u5e94\u4e2d\u7684\u5173\u952e\u4e2d\u95f4\u4f53\uff1b\u540c\u65f6\uff0c\u4f5c\u8005\u53d1\u73b0\u5728\u6ca1\u6709\u6c27\u6c14\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u8be5\u53cd\u5e94\u4e0d\u80fd\u751f\u6210\u76ee\u6807\u4ea7\u7269\uff0c\u8fd9\u8868\u660e\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u809f\u4e2d\u95f4\u4f53\u53ef\u80fd\u7531\u76f8\u5e94\u7684\u919b\u751f\u6210\u3002\u57fa\u4e8e\u8fd9\u4e9b\u5047\u8bbe\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4ee5\u4e0b\u53ef\u80fd\u7684\u50ac\u5316\u73af\uff08Fig.2, Cycle A\uff09\uff1a\u5e95\u72691(E1\/2<\/sub>(1\/1\u2022+<\/sup>) = +2.45 V vs.SCE\uff09\u88ab\u6fc0\u53d1\u6001\u7684\u5149\u50ac\u5316\u5242\u6c27\u5316\u751f\u6210\u81ea\u7531\u57fa\u9633\u79bb\u5b50II\u2022+<\/sup>\u548c\u88ab\u8fd8\u539f\u7684\u5149\u50ac\u5316\u5242\u7269\u79cd\uff08PC-4\u2022<\/sup>\uff09\uff1b\u63a5\u7740PC-4\u2022<\/sup>\u4e0eO2<\/sub>\u53d1\u751f\u5355\u7535\u5b50\u8f6c\u79fb\u5f62\u6210\u8d85\u6c27\u8d1f\u79bb\u5b50O2<\/sub>.-<\/sup>\uff1b\u4e2d\u95f4\u4f53\u9633\u79bb\u5b50\u81ea\u7531\u57faII.+<\/sup>\u5931\u53bb\u4e00\u4e2a\u8d28\u5b50\u751f\u6210\u66f4\u7a33\u5b9a\u7684\u82c4\u57fa\u81ea\u7531\u57faIII\u2022<\/sup>\uff0c\u63a5\u7740\u4e0e\u8d85\u6c27\u8d1f\u79bb\u5b50\u7ed3\u5408\u540c\u65f6\u8d28\u5b50\u5316\u751f\u6210\u8fc7\u6c27\u5316\u7269V\uff1b\u53e6\u5916\u4e00\u79cd\u53ef\u80fd\u662f\u82c4\u57fa\u81ea\u7531\u57faIII\u2022\u76f4\u63a5\u4e0e\u6c27\u6c14\u7ed3\u5408\u751f\u6210\u8fc7\u6c27\u81ea\u7531\u57fa\uff0c\u518d\u4ecePC-4\u2022<\/sup>\u83b7\u5f97\u4e00\u4e2a\u7535\u5b50\u751f\u6210\u4e2d\u95f4\u4f53V\uff1b\u4e2d\u95f4\u4f53V\u8131\u6c34\u751f\u6210\u919b\u4e2d\u95f4\u4f53VI\uff0c\u919b\u518d\u4e0e\u7f9f\u80fa\u7f29\u5408\u751f\u6210\u809f\u4e2d\u95f4\u4f53VII\uff1b\u4e2d\u95f4\u4f53VII\u8fdb\u5165\u5149\u50ac\u5316\u5faa\u73afCycle A\u2019\uff0cVII\u88ab\u6fc0\u53d1\u6001\u7684\u5149\u50ac\u5316\u5242\u6c27\u5316\u751f\u6210VIII.+<\/sup>\uff0c\u63a5\u7740\u8131\u6c34\u751f\u6210IX.+<\/sup>\uff0c\u88ab\u8fd8\u539f\u7684\u5149\u50ac\u5316\u5242\u4e0eIX.+<\/sup>\u53d1\u751f\u5355\u7535\u5b50\u8f6c\u79fb\u8fc7\u7a0b\u751f\u6210\u76ee\u6807\u4ea7\u7269X\uff0c\u540c\u65f6\u5173\u95ed\u50ac\u5316\u73af\uff08Fig.2, Cycle A\u2019\uff09\u3002\u7531\u4e8e\u6eb4\u5316\u94f5\u5728\u8be5\u53cd\u5e94\u4e2d\u8d77\u5230\u4e86\u4e00\u79cd\u975e\u5e38\u5173\u952e\u7684\u4f5c\u7528\uff0c\u6240\u4ee5\u53ef\u80fd\u5b58\u5728\u53e6\u5916\u4e00\u79cd\u50ac\u5316\u5faa\u73af\uff08Fig.2, Cycle B\uff09\uff1a\u5728\u53ef\u89c1\u5149\u7167\u5c04\u4e0b\uff0c\u6fc0\u53d1\u6001\u7684PC\u5c06Br–<\/sup>\u8d1f\u79bb\u5b50\u6c27\u5316\u6210Br\u2022\u81ea\u7531\u57fa\uff0cBr\u2022\u81ea\u7531\u57fa\u4ece\u5e95\u7269\u652b\u53d6\u4e00\u4e2a\u6c22\u539f\u5b50\u751f\u6210\u82c4\u57fa\u81ea\u7531\u57faIII\u2022<\/sup>\u548cHBr\uff0c\u82c4\u57fa\u81ea\u7531\u57faIII.\u4e0e\u8d85\u6c27\u8d1f\u79bb\u5b50\u751f\u6210IV-\u4e2d\u95f4\u4f53\uff0c\u518d\u88abHBr\u8d28\u5b50\u5316\u751f\u6210\u4e2d\u95f4\u4f53V, \u4e2d\u95f4\u4f53V\u8fdb\u5165Cycle A\u548cCycle A\u2019\u6240\u793a\u7684\u5faa\u73af\u3002\u4f5c\u8005\u8fd8\u901a\u8fc7\u65f6\u95f4\u5206\u8fa8\u8367\u5149\u731d\u706d\u5b9e\u9a8c\u548c\u673a\u7406\u63a7\u5236\u5b9e\u9a8c\u652f\u6491\u4e86\u4ee5\u4e0a\u50ac\u5316\u5faa\u73af\u5047\u8bbe\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u5e95\u7269\u62d3\u5c55<\/strong><\/span>
\n\u5728\u786e\u5b9a\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5bf9\u7532\u57fa\u82b3\u70c3\u7c7b\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u63a2\u7d22\uff08Scheme 2\uff09\u3002\u4f5c\u8005\u53d1\u73b0\u65e0\u8bba\u662f\u5438\u7535\u5b50\u57fa\u8fd8\u662f\u7ed9\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u5e95\u7269\u5747\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u4ea7\u7387\u751f\u6210\u76ee\u6807\u4ea7\u7269\uff08Scheme 2, 5-39\uff09\uff0c\u5982\u7fa7\u9178\u3001\u916f\u3001\u9170\u80fa\u3001\u5364\u7d20\u3001\u6c30\u5316\u7269\u548c\u787c\u9178\u916f\u5747\u80fd\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff08Scheme 2, 5-6, 9-12, 15-18 and 22-23\uff09\uff1b\u5229\u7528\u8fd9\u79cd\u53cd\u5e94\u65b9\u6cd5\u53ef\u4ee5\u4e00\u9505\u5408\u6210\u53cc\u8148\u7c7b\u5316\u5408\u726924\uff1b\u6b64\u5916\uff0c\u4e00\u4e9b\u5177\u6709\u751f\u7269\u6d3b\u6027\u548c\u836f\u7269\u6d3b\u6027\u7684\u590d\u6742\u5206\u5b50\u4e5f\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u4ea7\u7387\u751f\u6210\u6c30\u57fa\u5316\u4ea7\u7269\uff0829-39\uff09\uff1b\u6709\u8da3\u7684\u662f\uff0c\u4e00\u4e9b\u5728\u6c27\u6c14\u5b58\u5728\u7684\u5149\u5316\u5b66\u53cd\u5e94\u6761\u4ef6\u4e0b\u4e0d\u7a33\u5b9a\u7684\u542b\u591a\u4e2a\u6c27\u539f\u5b50\u7684\u5e95\u7269\uff0c\u5982\u7cd6\u7c7b\u884d\u751f\u726929\u4e0e38\u4e5f\u80fd\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u5206\u522b\u4ee562%\u548c60%\u7684\u4ea7\u7387\u751f\u6210\u76ee\u6807\u4ea7\u7269\u3002\u800c\u4e14\uff0c\u4e00\u4e9b\u66f4\u590d\u6742\u7684\u5206\u5b50\uff0c\u5982\u80c6\u56fa\u9187\u3001\u5f02\u51b0\u7247\u3001\u6c28\u57fa\u9178\u4ee5\u53ca\u80bd\u7c7b\u884d\u751f\u7269\u4e5f\u80fd\u4ee545-70%\u7684\u4ea7\u7387\u751f\u6210\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u7269\uff1b\u66f4\u6709\u8da3\u7684\u662f\uff0c\u6d88\u708e\u836f\u585e\u6765\u6614\u5e03\u4e5f\u80fd\u4ee570%\u7684\u4ea7\u7387\u751f\u6210\u76ee\u6807\u4ea7\u7269\uff08Celecoxib\uff0c37\uff09\uff1b\u540c\u65f6\uff0c\u5316\u5408\u72692\u548c\u585e\u6765\u6614\u5e03\uff0837\uff09\u5728\u8fdb\u884c\u514b\u7ea7\u53cd\u5e94\u65f6\u80fd\u5206\u522b\u4ee565%\u548c60%\u7684\u4ea7\u7387\u751f\u6210\u6c30\u57fa\u5316\u4ea7\u7269\u3002
\n\u4f5c\u8005\u5728\u5bf9\u7532\u57fa\u82b3\u70c3\u7c7b\u5e95\u7269\u8fdb\u884c\u63a2\u7d22\u540e\uff0c\u7ee7\u7eed\u5bf9\u8be5\u65b9\u6cd5\u5728\u9187\u3001\u919b\u548c\u809f\u7c7b\u5e95\u7269\u7684\u53cd\u5e94\u9002\u7528\u6027\u8fdb\u884c\u4e86\u63a2\u7d22\uff08Scheme 3\uff09\u3002\u4e0e\u7532\u57fa\u82b3\u70c3\u7c7b\u5e95\u7269\u7c7b\u4f3c\uff0c\u9187\u3001\u919b\u548c\u809f\u7c7b\u5e95\u7269\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e0b\u4e5f\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u4ea7\u7387\uff0845-90%\uff09\u83b7\u5f97\u76f8\u5e94\u7684\u6c30\u57fa\u5316\u4ea7\u7269\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u95f4\u82ef\u4e8c\u7532\u919b\u53d1\u751f\u4e24\u6b21\u6c30\u5316\u53cd\u5e94\u4ee578%\u7684\u4ea7\u7387\u83b7\u5f97\u95f4\u82ef\u4e8c\u8148\u4ea7\u726944\uff1b\u4f4d\u963b\u8f83\u5927\u76842,6-\u4e8c\u6c2f\u82ef\u7532\u919b\u4e5f\u80fd\u4ee582%\u7684\u4f18\u79c0\u4ea7\u7387\u53cd\u5e94\u83b7\u5f972,6-\u4e8c\u6c2f\u82ef\u8148\uff08DCBN, 45\uff09\u3002<\/p>\n

\"\"\"\"<\/a><\/p>\n

\u603b\u7ed3\u4e0e\u8bc4\u4ef7<\/h4>\n

Burkhard K\u00f6nig\u6559\u6388\u8bfe\u9898\u7ec4\u5b9e\u73b0\u4e86\u7b2c\u4e00\u4f8b\u65e0\u91d1\u5c5e\u3001\u6c30\u5316\u7269\u7684\u53ef\u89c1\u5149\u8bf1\u5bfc\u7684\u6709\u673a\u5149\u50ac\u5316\u5242\u50ac\u5316\u7684C(sp3<\/sup>)-H\u952e\u80fa\u6c27\u5316\u53cd\u5e94\u3002\u8be5\u65b9\u6cd5\u4ee5\u7f9f\u80fa\u76d0\u9178\u76d0\u4f5c\u4e3a\u6c2e\u6e90\u3001\u6eb4\u5316\u94f5\u4e3a\u6dfb\u52a0\u5242\u3001\u6c27\u6c14\u4f5c\u4e3a\u6c27\u5316\u5242\uff0c\u5728\u6e29\u548c\u7684\u53cd\u5e94\u6761\u4ef6\u4e0b\u5c31\u80fd\u5b9e\u73b0C(sp3<\/sup>)-H\u952e\u7684\u80fa\u6c27\u5316\u53cd\u5e94\uff0c\u907f\u514d\u4e86\u9ad8\u6e29\u3001\u8fc7\u6e21\u91d1\u5c5e\u548c\u9ad8\u6bd2\u6027\u6c30\u5316\u7269\u7684\u4f7f\u7528\uff1b\u8be5\u53cd\u5e94\u65b9\u6cd5\u7684\u5e95\u7269\u666e\u9002\u6027\u8f83\u5e7f\u3001\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u4e5f\u8f83\u597d\uff1b\u540c\u65f6\uff0c\u4f5c\u8005\u8fd8\u8fdb\u884c\u4e86\u514b\u7ea7\u89c4\u6a21\u53cd\u5e94\u8bc1\u660e\u4e86\u8be5\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fd8\u5bf9\u8be5\u53cd\u5e94\u7684\u673a\u7406\u8fdb\u884c\u4e86\u4ed4\u7ec6\u7814\u7a76\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/h4>\n[1] a) Z. Shu, Y. Ye, Y. Deng, Y. Zhang, J. Wang, Angew. Chem. Int. Ed.<\/em> 2013<\/strong>, 52, 10573. DOI: 10.1002\/anie.201305731; b) J. Liu, H.-X. Zheng, C.-Z. Yao, B.-F. Sun, Y.-B. Kang, J. Am. Chem. Soc.<\/em> 2016<\/strong>, 138, 3294. DOI: 10.1021\/jacs.6b00180; c) W. Zhou, L. Zhang, N. Jiao, Angew. Chem. Int. Ed<\/em>. 2009<\/strong>, 48, 7094. DOI: 10.1002\/anie.200903838.
\n[2] J.Nandi, M. L. Witko, N. E. Leadbeater, Synlett<\/em>. 2018<\/strong>, 29, 2185. DOI: 10.1055\/s-0037-1610272.
\n[3] F. Verma, P. Shukla, S. R. Bhardiya, M. Singh, A. Rai, V. K. Rai, Catal. Commun<\/em>. 2019<\/strong>, 119, 76. DOI: 10.1016\/j.catcom.2018.10.031.
\n[4] T. Alam, A. Rakshit, P. Begum, A. Dahiya, B. K. Patel, Org. Lett<\/em>. 2020<\/strong>, 22, 3728. DOI: 10.1021\/acs.orglett.0c01235.<\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1aChemBoy \u5bfc\u8bfb \u5728\u6709\u673a\u5408\u6210\u4e2d\uff0cC(sp3)-H\u952e\u5728\u975e\u91d1\u5c5e\u6d3b\u5316\u4f5c\u7528\u4e0b\u8f6c\u5316\u6210\u9ad8\u9644\u52a0\u503c\u5316\u5408\u7269\u662f\u4e00\u4e2a\u975e\u5e38\u91cd\u8981\u7684\u7814\u7a76\u9886\u57df\u3002\u6700\u8fd1\uff0c\u5fb7\u56fd\u96f7\u6839\u65af\u5821\u5927\u5b66Burkhard K\u00f6nig\u6559\u6388\u8bfe\u9898\u7ec4\u5229\u7528\u5546\u4e1a\u53ef\u5f97\u7684\u6709\u673a\u67d3\u65992,4,6-\u4e09\u82ef\u57fa\u5421\u5576\u56db\u6c1f\u787c\u9178\u76d0\uff08TPP\uff09\u4f5c\u4e3a\u5149\u654f\u5242\uff0c\u5728\u53ef\u89c1\u5149\u8f90\u5c04\u6761\u4ef6\u4e0b\u5b9e\u73b0\u4e86\u4eceC(sp3)-H\u952e\u8f6c\u5316\u6210\u6c30\u57fa\u7684\u65b9\u6cd5\uff0c\u901a\u8fc7\u8fd9\u79cd\u65b9\u6cd5\u53ef\u4ee5\u4ece\u7532\u57fa\uff08\u6742\uff09\u82b3\u70c3\u5408\u6210\u4e00\u7cfb\u5217\u7684\uff08\u6742\uff09\u82b3\u8148\u5316\u5408\u7269\u3002\u4ed6\u4eec\u7684\u65b9\u6cd5\u907f\u514d\u4e86\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u548c\u6709\u6bd2\u6c30\u5316\u7269\u7684\u4f7f\u7528\uff0c\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u5728\u300aAngew. Chem. Int. Ed.\u300b\u4e0a\uff1a \u201cVisible-Light-Promoted Metal-Free Synthesis of (Hetero)aromatic Nitriles from C(sp3)-H bonds\u201d Kathiravan Murugesan, Karsten Donabauer, and Burkhard K\u00f6nig* Angew. Chem. Int. Ed. 2020, Accepted Articles, 10.1002\/anie.202011815\u00a0https:\/\/doi.org\/10.1002\/anie.202011815 \u6b63\u6587 \u524d\u8a00 \u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u5728\u4e00\u4e9b\u5de5\u4e1a\u751f\u4ea7\u3001\u7cbe\u7ec6\u5316\u5b66\u54c1\u548c\u5927\u5b97\u5316\u5b66\u54c1\u7684\u5408\u6210\u53cd\u5e94\u4e2d\u662f\u4e0d\u53ef\u6216\u7f3a\u7684\u3002\u5728\u8fc7\u53bb\u4e8c\u5341\u5e74\u91cc\uff0c\u4e00\u4e9b\u901a\u8fc7\u70ed\u5316\u5b66\u6216\u5149\u5316\u5b66\u9014\u5f84\u8fdb\u884c\u7684C(sp3)-H\u952e\u6d3b\u5316\u7684\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u5df2\u7ecf\u88ab\u53d1\u5c55\u3002\u5176\u4e2d\u4e00\u79cd\u91cd\u8981\u7684\u8f6c\u5316\u5c31\u662f\u5c06\u77f3\u6cb9\u5316\u5de5\u526f\u4ea7\u54c1\u8f6c\u5316\u6210\u7cbe\u7ec6\u5316\u5b66\u54c1\uff0c\u6bd4\u5982\u4ece\u7532\u82ef\u5408\u6210\u82ef\u8148\u7684\u8f6c\u5316\u3002\u5728\u5de5\u4e1a\u4e0a\uff0c\u82ef\u8148\u662f\u901a\u8fc7\u7532\u82ef\u5728\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\uff08\u9492\uff09\u4f5c\u7528\u4e0b\u3001\u6c28\u6c14\u548c\u6c27\u6c14\u9ad8\u538b\u9ad8\u6e29\uff08300-500 \u00baC\uff09\u6761\u4ef6\u4e0b\u53d1\u751f\u80fa\u6c27\u5316\u53cd\u5e94\u5236\u5907\u3002\u56e0\u4e3a\u6c30\u57fa\u4e0d\u4ec5\u662f\u5404\u79cd\u836f\u7269\u548c\u751f\u7269\u6d3b\u6027\u5206\u5b50\u4e2d\u7684\u5173\u952e\u5b98\u80fd\u56e2\u3001\u8fd8\u662f\u4e00\u4e9b\u7cbe\u7ec6\u548c\u5927\u5b97\u5316\u5b66\u54c1\u7684\u91cd\u8981\u5408\u6210\u780c\u5757\u3002\u6240\u4ee5\uff0c\u8fd1\u5e74\u6765\uff0c\u4e00\u4e9b\u65b0\u7684\u3001\u6761\u4ef6\u6e29\u548c\u7684\u3001\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\u4ece\u9187\u3001\u80fa\u3001\u919b\u6216\u662f\u7b80\u5355CH3\u5408\u6210\u6c30\u57fa\u5316\u5408\u7269\u7684\u53cd\u5e94\u65b9\u6cd5\u5df2\u7ecf\u88ab\u62a5\u9053[1]\u3002\u7136\u800c\uff0c\u5728\u8fd9\u4e9b\u65b9\u6cd5\u4e2d\uff0c\u5f88\u591a\u60c5\u51b5\u4e0b\u90fd\u9700\u8981\u5728\u8f83\u9ad8\u7684\u6e29\u5ea6\u4e0b\u53cd\u5e94\u3001\u751a\u81f3\u7ecf\u5e38\u9700\u8981\u4f7f\u7528\u9ad8\u6bd2\u6027\u7684\u6c30\u5316\u7269\u4f5c\u4e3a\u6c30\u57fa\u6e90\uff0c\u6216\u8005\u662f\u9700\u8981\u4f7f\u7528\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u3002\u9274\u4e8e\u8fd9\u4e9b\u65b9\u6cd5\u6240\u7528\u8bd5\u5242\u7684\u9ad8\u6210\u672c\u3001\u9ad8\u6bd2\u6027\u7b49\u7f3a\u70b9\uff0c\u53d1\u5c55\u65e0\u91d1\u5c5e\u50ac\u5316\u3001\u65e0\u6c30\u5316\u7269\u4f5c\u4e3a\u6c30\u57fa\u6e90\u3001\u5c24\u5176\u662f\u76f4\u63a5\u4eceC-H\u952e\u8f6c\u5316\u4e3a\u6c30\u57fa\u7684\u53cd\u5e94\u65b9\u6cd5\u662f\u975e\u5e38\u6709\u5fc5\u8981\u7684\u3002 \u8fd1\u5e74\u6765\uff0c\u51e0\u4f8b\u4f7f\u7528\u66f4\u7eff\u8272\u7684\u94f5\u76d0\u4f5c\u4e3a\u6c2e\u6e90\u3001\u901a\u8fc7\u5149\u5316\u5b66\u65b9\u6cd5\u5408\u6210\u8148\u7c7b\u5316\u5408\u7269\u7684\u53cd\u5e94\u5f97\u5230\u62a5\u9053\u3002\u5305\u62ec\u5229\u7528\u8fc7\u786b\u9178\u94f5\u4e3a\u6c2e\u6e90\u3001\u82b3\u919b\u5728\u948c\u5149\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u751f\u6210\u82b3\u8148\uff08Scheme 1A\uff09[2]\u6216\u8005\u662f\u82b3\u919b\u4e0e\u7f9f\u80fa\u76d0\u9178\u76d0\u5728\u591a\u76f8\u5149\u50ac\u5316\u5242Co@g-C3N4\u4f5c\u7528\u4e0b\u751f\u6210\u82b3\u8148\u7684\u53cd\u5e94\uff08Scheme 1B\uff09[3]\uff1b\u53e6\u5916\u4e00\u4f8b\u975e\u5e38\u6709\u610f\u601d\u7684\u53cd\u5e94\u662f\u82ef\u4e59\u70ef\u8f6c\u5316\u6210\u6c30\u57fa\u809f\u7684\u53cd\u5e94\uff08Scheme 1C\uff09[4]\u3002\u8fd9\u4e9b\u5149\u50ac\u5316\u5408\u6210\u6c30\u57fa\u7c7b\u5316\u5408\u7269\u7684\u53cd\u5e94\u90fd\u6210\u529f\u907f\u514d\u4e86\u9ad8\u6bd2\u6027\u6c30\u5316\u7269\u7684\u4f7f\u7528\u3002\u7136\u800c\uff0c\u7532\u57fa\u82b3\u70c3\u76f4\u63a5\u8f6c\u5316\u6210\u6c30\u57fa\u5316\u5408\u7269\u5bf9\u4e8e\u5de5\u4e1a\u7684\u6c28\u6c27\u5316\u53cd\u5e94\u6765\u8bf4\u662f\u66f4\u7b80\u5355\u6709\u6548\u5408\u6210\u8def\u5f84\u3002 \u57fa\u4e8e\u4ee5\u4e0a\u4e00\u4e9b\u56e0\u7d20\uff0c\u4f5c\u8005\u8bbe\u60f3\u662f\u5426\u53ef\u4ee5\u5229\u7528\u4e00\u79cd\u975e\u91d1\u5c5e\u5149\u50ac\u5316\u5242\u3001\u540c\u65f6\u65e0\u9700\u6c30\u5316\u7269\u4f5c\u4e3a\u6c30\u57fa\u6e90\uff0c\u76f4\u63a5\u5c06\u7532\u82ef\u4e00\u6b65\u8f6c\u5316\u4e3a\u82b3\u8148\u3002\u4f5c\u8005\u5047\u8bbe\uff0c\u7532\u57fa\u82b3\u70c3\uff08\u7532\u82ef\u7684\u6c27\u5316\u7535\u52bf\u4e3aE1\/2 = +2.36 V vs.SCE\uff09\u53ef\u80fd\u4f1a\u88ab\u9ad8\u6c27\u5316\u6027\u7684\u5149\u50ac\u5316\u5242\u6d3b\u5316\u6216\u662f\u652b\u53d6\u82c4\u4f4d\u6c22\u539f\u5b50\u3002\u4f5c\u8005\u5728\u8fd9\u91cc\u5229\u7528\u4e00\u79cd\u5546\u4e1a\u53ef\u5f97\u7684\u6709\u673a\u67d3\u65992,4,6-\u4e09\u82ef\u57fa\u5421\u5576\u56db\u6c1f\u787c\u9178\u76d0\uff08TPP\uff09\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\u3001\u7f9f\u80fa\u76d0\u9178\u76d0\u4f5c\u4e3a\u80fa\u6e90\u3001\u6eb4\u5316\u94f5\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u5728\u6c27\u6c14\u6c1b\u56f4\u4e2d\u3001\u53ef\u89c1\u5149\u8f90\u5c04\u4e0b\u5b9e\u73b0\u4e86\u4ece\u7532\u82ef\u4e00\u6b65\u5408\u6210\u82b3\u8148\u7684\u53cd\u5e94\u3002 \u6761\u4ef6\u4f18\u5316 \u5728\u8fd9\u91cc\uff0c\u4f5c\u8005\u4ee54-\u7532\u57fa\u82ef\u7532\u9178\u7532\u916f1\u4f5c\u4e3a\u6a21\u677f\u5e95\u7269\u5bf9\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u4f18\u5316\uff08Table 1\uff09\u3002\u4f5c\u8005\u4ee5NH2OH\u2022HCl\u4f5c\u4e3a\u6c2e\u6e90\u3001NH4Br\u4f5c\u4e3a\u6dfb\u52a0\u5242\u3001\u6c27\u6c14\u4f5c\u4e3a\u6c27\u5316\u5242\u3001\u4e59\u8148\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u572840 \u00baC\u7684\u53cd\u5e94\u6e29\u5ea6\u3001\u6ce2\u957f\u4e3a455 nm\u7684\u53ef\u89c1\u5149\u7167\u5c04\u6761\u4ef6\u4e0b\uff0c\u5bf9\u4e00\u7cfb\u5217\u5546\u4e1a\u53ef\u5f97\u7684\u6709\u673a\u67d3\u6599\u8fdb\u884c\u4e86\u7b5b\u9009\u3002\u4f7f\u7528DDQ (PC-1)\u548c\u5416\u5576\u7c7b\u5149\u50ac\u5316\u5242\uff08PC-2\u3001PC-3\uff09\u65f6\uff0c\u5747\u80fd\u68c0\u6d4b\u5230\u76ee\u6807\u4ea7\u7269\uff0c\u4f46\u662f\u4ea7\u7387\u5f88\u4f4e\uff0812-26%\uff0cTable 1,entries 1-3\uff09\u3002\u4ee4\u4eba\u9ad8\u5174\u7684\u662f\uff0c\u5f53\u4f7f\u7528TPP(PC-4\uff0cE1\/2 = +2.55 V vs. SCE)\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\u65f6\u80fd\u4ee576%\u7684\u4ea7\u7387\u83b7\u5f97\u76ee\u6807\u4ea7\u72694-\u6c30\u57fa\u82ef\u7532\u9178\u7532\u916f2\uff08Table 1,entry 4\uff09\u3002\u4f5c\u8005\u8fd8\u5bf9\u5176\u4ed6\u6c2e\u6e90\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u5982\u4e59\u9178\u94f5\u548c\u6c28\u6c34\u5747\u6ca1\u6709\u68c0\u6d4b\u5230\u76ee\u6807\u4ea7\u7269\uff08Table 1,entry 5 and entry 6\uff09\uff0c\u4f5c\u8005\u8ba4\u4e3a\u8fd9\u79cd\u73b0\u8c61\u53ef\u80fd\u662f\u56e0\u4e3a\u8fd9\u79cd\u7b80\u5355\u94f5\u79bb\u5b50\u88ab\u6c27\u5316\u7684\u901f\u7387\u6bd4\u76ee\u6807\u5e95\u7269\u88ab\u6c27\u5316\u7684\u901f\u7387\u5feb\u4ee5\u53caPC-4\u5728\u78b1\u6216\u4eb2\u6838\u8bd5\u5242\u5b58\u5728\u6761\u4ef6\u4e0b\u4f1a\u5206\u89e3\u7b49\u539f\u56e0\u5bfc\u81f4\u7684\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u901a\u8fc7\u63a7\u5236\u5b9e\u9a8c\u53d1\u73b0\uff0c\u5149\u3001\u5149\u50ac\u5316\u5242\u3001\u6c27\u6c14\u548c\u7f9f\u80fa\u76d0\u9178\u76d0\u5bf9\u8be5\u53cd\u5e94\u7684\u987a\u5229\u8fdb\u884c\u81f3\u5173\u91cd\u8981\u3002 \u5728\u786e\u5b9a\u4e86\u5149\u50ac\u5316\u5242\u540e\uff0c\u4f5c\u8005\u8fd8\u5bf9\u53cd\u5e94\u6e29\u5ea6\u3001\u6eb4\u5316\u94f5\u548c\u7f9f\u80fa\u7684\u8d1f\u8f7d\u91cf\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\u8fdb\u884c\u4e86\u4ed4\u7ec6\u7684\u7814\u7a76\uff08Fig. 1\uff09\u3002\u5728\u4f4e\u6e29\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f1a\u6291\u5236\u526f\u4ea7\u7269\u809f3\u8131\u6c34\u751f\u6210\u76ee\u6807\u4ea7\u72692\uff08Fig.1a\uff09\uff1b\u6dfb\u52a0\u5242\u6eb4\u5316\u94f5\u7684\u5b58\u5728\u80fd\u591f\u6709\u6548\u4fc3\u8fdb\u53cd\u5e94\u7684\u8fdb\u884c\uff08Fig.1b\uff09;\u6b64\u5916\uff0c\u65e0\u5408\u9002\u7684\u6c2e\u6e90\u5b58\u5728\u6761\u4ef6\u4e0b\uff0c\u4f1a\u53d1\u751f\u8fc7\u5ea6\u6c27\u5316\u53cd\u5e94\u751f\u6210\u7fa7\u91784\uff08Fig.1c\uff09\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u809f3\u53ea\u6709\u5728\u5149\u50ac\u5316\u6761\u4ef6\u4e0b\u624d\u80fd\u8f6c\u5316\u751f\u6210\u76ee\u6807\u4ea7\u72692\uff08Fig.1d\uff09\u3002 \u673a\u7406\u5047\u8bbe \u901a\u8fc7\u6761\u4ef6\u7b5b\u9009\uff0c\u4f5c\u8005\u53d1\u73b0\u809f3\u662f\u8be5\u53cd\u5e94\u4e2d\u7684\u5173\u952e\u4e2d\u95f4\u4f53\uff1b\u540c\u65f6\uff0c\u4f5c\u8005\u53d1\u73b0\u5728\u6ca1\u6709\u6c27\u6c14\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u8be5\u53cd\u5e94\u4e0d\u80fd\u751f\u6210\u76ee\u6807\u4ea7\u7269\uff0c\u8fd9\u8868\u660e\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u809f\u4e2d\u95f4\u4f53\u53ef\u80fd\u7531\u76f8\u5e94\u7684\u919b\u751f\u6210\u3002\u57fa\u4e8e\u8fd9\u4e9b\u5047\u8bbe\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4ee5\u4e0b\u53ef\u80fd\u7684\u50ac\u5316\u73af\uff08Fig.2, Cycle A\uff09\uff1a\u5e95\u72691(E1\/2(1\/1\u2022+) = +2.45 V vs.SCE\uff09\u88ab\u6fc0\u53d1\u6001\u7684\u5149\u50ac\u5316\u5242\u6c27\u5316\u751f\u6210\u81ea\u7531\u57fa\u9633\u79bb\u5b50II\u2022+\u548c\u88ab\u8fd8\u539f\u7684\u5149\u50ac\u5316\u5242\u7269\u79cd\uff08PC-4\u2022\uff09\uff1b\u63a5\u7740PC-4\u2022\u4e0eO2\u53d1\u751f\u5355\u7535\u5b50\u8f6c\u79fb\u5f62\u6210\u8d85\u6c27\u8d1f\u79bb\u5b50O2.-\uff1b\u4e2d\u95f4\u4f53\u9633\u79bb\u5b50\u81ea\u7531\u57faII.+\u5931\u53bb\u4e00\u4e2a\u8d28\u5b50\u751f\u6210\u66f4\u7a33\u5b9a\u7684\u82c4\u57fa\u81ea\u7531\u57faIII\u2022\uff0c\u63a5\u7740\u4e0e\u8d85\u6c27\u8d1f\u79bb\u5b50\u7ed3\u5408\u540c\u65f6\u8d28\u5b50\u5316\u751f\u6210\u8fc7\u6c27\u5316\u7269V\uff1b\u53e6\u5916\u4e00\u79cd\u53ef\u80fd\u662f\u82c4\u57fa\u81ea\u7531\u57faIII\u2022\u76f4\u63a5\u4e0e\u6c27\u6c14\u7ed3\u5408\u751f\u6210\u8fc7\u6c27\u81ea\u7531\u57fa\uff0c\u518d\u4ecePC-4\u2022\u83b7\u5f97\u4e00\u4e2a\u7535\u5b50\u751f\u6210\u4e2d\u95f4\u4f53V\uff1b\u4e2d\u95f4\u4f53V\u8131\u6c34\u751f\u6210\u919b\u4e2d\u95f4\u4f53VI\uff0c\u919b\u518d\u4e0e\u7f9f\u80fa\u7f29\u5408\u751f\u6210\u809f\u4e2d\u95f4\u4f53VII\uff1b\u4e2d\u95f4\u4f53VII\u8fdb\u5165\u5149\u50ac\u5316\u5faa\u73afCycle A\u2019\uff0cVII\u88ab\u6fc0\u53d1\u6001\u7684\u5149\u50ac\u5316\u5242\u6c27\u5316\u751f\u6210VIII.+\uff0c\u63a5\u7740\u8131\u6c34\u751f\u6210IX.+\uff0c\u88ab\u8fd8\u539f\u7684\u5149\u50ac\u5316\u5242\u4e0eIX.+\u53d1\u751f\u5355\u7535\u5b50\u8f6c\u79fb\u8fc7\u7a0b\u751f\u6210\u76ee\u6807\u4ea7\u7269X\uff0c\u540c\u65f6\u5173\u95ed\u50ac\u5316\u73af\uff08Fig.2, Cycle A\u2019\uff09\u3002\u7531\u4e8e\u6eb4\u5316\u94f5\u5728\u8be5\u53cd\u5e94\u4e2d\u8d77\u5230\u4e86\u4e00\u79cd\u975e\u5e38\u5173\u952e\u7684\u4f5c\u7528\uff0c\u6240\u4ee5\u53ef\u80fd\u5b58\u5728\u53e6\u5916\u4e00\u79cd\u50ac\u5316\u5faa\u73af\uff08Fig.2, Cycle 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