{"id":154511,"date":"2018-09-26T08:00:16","date_gmt":"2018-09-26T00:00:16","guid":{"rendered":"http:\/\/www.cailiaoniu.com\/?p=154511"},"modified":"2018-09-26T09:05:54","modified_gmt":"2018-09-26T01:05:54","slug":"%e9%ad%8f%e8%8c%a8%e6%9b%bc%e7%a0%94%e7%a9%b6%e6%89%80jacs-%e7%94%b5%e5%8c%96%e5%ad%a6%e8%bf%98%e5%8e%9f%e4%b8%ad%e7%9a%84%e9%ab%98%e6%b4%bb%e6%80%a7%e5%82%ac%e5%8c%96%e5%89%82","status":"publish","type":"post","link":"http:\/\/www.cailiaoniu.com\/?p=154511","title":{"rendered":"\u9b4f\u8328\u66fc\u7814\u7a76\u6240JACS: \u7535\u5316\u5b66\u8fd8\u539f\u4e2d\u7684\u9ad8\u6d3b\u6027\u50ac\u5316\u5242\u2014\u2014\u4e8c\u914d\u4f4d\u5c42\u786b\u8132"},"content":{"rendered":"

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

\u8fd1\u5e74\u6765\uff0c\u4eba\u4eec\u5bf9\u4e8c\u6c27\u5316\u78b3\u7684\u7535\u5316\u5b66\u8fd8\u539f\u8fdb\u884c\u4e86\u5e7f\u6cdb\u7684\u7814\u7a76\uff0c\u671f\u671b\u901a\u8fc7\u7406\u89e3\u8be6\u7ec6\u7684\u673a\u7406\u4ece\u800c\u5b9e\u73b0\u627e\u5230\u5177\u6709\u9ad8\u8f6c\u6362\u6548\u7387\u548c\u4f4e\u8fd8\u539f\u7535\u4f4d\u7684\u7a33\u5b9a\u50ac\u5316\u5242\u7684\u76ee\u6807\u3002\u540c\u65f6\uff0c\u786b\u8132\u4f5c\u4e3a\u4e00\u7c7b\u6709\u673a\u50ac\u5316\u5242\uff0c\u5c24\u5176\u662f\u90a3\u4e9b\u88ab\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u90a3\u4e9b\uff0c\u5982PhCF3<\/sub>\uff0c\u662f\u901a\u8fc7\u4e0e\u5404\u79cd\u5b98\u80fd\u56e2\uff08\u5982\u785d\u57fa\uff0c\u4e9a\u80fa\u548c\u7fb0\u57fa\uff09\u5f62\u6210\u6c22\u952e\u4ece\u800c\u4fc3\u8fdb\u53cd\u5e94\u7684\u3002\u6700\u8fd1\uff0c\u7814\u7a76\u4eba\u5458\u53d1\u73b0\u4e86\u4e00\u79cd\u4e0e\u8be5\u7cfb\u5217\u7684\u5176\u4ed6\u50ac\u5316\u5242\u76f8\u6bd4\uff0c\u5177\u6709\u9ad8\u8fbe3040 s-1<\/sup>\u7684\u8f6c\u6362\u9891\u7387\u7684\u9ad8\u6548\u50ac\u5316\u5242\u3002<\/p>\n

 <\/p>\n

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

\u00a0<\/strong>\u4ee5\u8272\u5217\u9b4f\u8328\u66fc\u79d1\u5b66\u7814\u7a76\u6240<\/strong>Ronny Neumann<\/strong>\u7b49<\/strong>\u7814\u7a76\u4eba\u5458\u901a\u8fc7\u4f7f\u7528\u8457\u540d\u7684fac-<\/em>Re(I)bipyridine(CO)3<\/sub>Cl\u914d\u5408\u7269\u4f5c\u4e3a\u8d77\u59cb\u70b9\uff0c\u5728\u5df2\u77e5\u786b\u8132\u7cfb\u94fe\u53ef\u4ee5\u4e0e\u7fb0\u57fa\u7ec4\u6210\u6c22\u952e\u7684\u60c5\u51b5\u4e0b\uff0c\u5728\u7b2c\u4e8c\u914d\u4f4d\u5c42\u5185\u7528\u786b\u8132\u7cfb\u94fe\u4fee\u9970\u4e86\u4e8c\u5421\u5576\u914d\u4f53\uff0c\u5f97\u5230\u4e86\u80fd\u5c06CO2<\/sub>\u9009\u62e9\u6027\u8fd8\u539f\u4e3aCO\u7684\u4f18\u5f02\u7684\u7535\u50ac\u5316\u5242\u2014\u2014Re(I)\u50ac\u5316\u5242\uff0c\u5176\u8f6c\u6362\u9891\u7387\u4e3a3040 s-1<\/sup>\u3002\u901a\u8fc71<\/sup>H NMR\u53ef\u4ee5\u89c2\u5bdf\u5230CO2<\/sub>\u4e0e\u786b\u8132\u7cfb\u94fe\u7684\u7ed3\u5408\uff0cNOE\u5b9e\u9a8c\u8868\u660e\u786b\u8132\u57fa\u56e2\u7684\u6c22\u539f\u5b50\u4e0d\u7a33\u5b9a\uff1b\u8fdb\u4e00\u6b65\u7684\u5b9e\u9a8c\u8868\u660e\uff0c\u786b\u8132\u90e8\u5206\u4e5f\u662f\u4e00\u4e2a\u5c40\u90e8\u8d28\u5b50\u6e90\uff0c\u5916\u52a0\u4e00\u4e2a\u5916\u90e8\u8d28\u5b50\u6e90\u5b9e\u9645\u4e0a\u6291\u5236\u4e86\u50ac\u5316\u3002\u901a\u8fc7DFT\u8ba1\u7b97\u53d1\u73b0\uff0c\u8d28\u5b50\u603b\u662f\u7ed3\u5408\u5230\u6700\u8fd1\u7684\u4e8c\u6c27\u5316\u78b3\u6c27\u539f\u5b50\u4e0a\uff0c\u5f62\u6210\u91d1\u5c5e\u7fa7\u9178\uff0c\u800c\u4e0d\u7ecf\u5386\u4efb\u4f55\u6700\u5c0f\u6216\u8fc7\u6e21\u72b6\u6001\uff0c\u4ece\u800c\u89e3\u91ca\u4e86\u52a8\u529b\u5b66\u540c\u4f4d\u7d20\u6548\u5e94\u7684\u7f3a\u5931\uff1b\u91c7\u7528EPR\u548cNMR\u5149\u8c31\u5bf9\u5404\u79cd\u8fd8\u539f\u4e2d\u95f4\u4f53\u8fdb\u884c\u4e86\u9274\u5b9a\u3002\u56e0\u6b64\u63d0\u51fa\uff0c\u56e0\u786b\u8132\u5728\u7b2c\u4e8c\u914d\u4f4d\u5c42\u7684\u675f\u7f1a\u53ef\u4ee5\u7ed3\u5408CO2<\/sub>\u3001\u7a33\u5b9a\u7fa7\u9178\u53cd\u5e94\u4e2d\u95f4\u4f53\u3001\u76f4\u63a5\u4f5c\u4e3a\u5c40\u90e8\u8d28\u5b50\u6e90\uff0c\u4ece\u800c\u5176\u660e\u663e\u662f\u66f4\u6d3b\u8dc3\u7684\u50ac\u5316\u5242\u3002\u8be5\u7814\u7a76\u53d1\u8868\u4e8eJournal of the American Chemical Society<\/strong>\uff0c\u9898\u4e3a\u201c<\/strong>A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO2<\/sub> and a Proton Donor Promotes the Electrochemical Reduction of CO2<\/sub> to CO Catalyzed by a Rhenium Bipyridine-Type Complex<\/strong>\u201d<\/strong>\u3002<\/p>\n

\u00a0<\/strong>\u3010\u56fe\u6587\u5bfc\u8bfb\u3011<\/strong><\/p>\n

\u00a0<\/strong>\u56fe<\/strong>1. DFT<\/strong>\u8ba1\u7b97<\/strong>Re(Bipy)(CO)3<\/sub><\/strong>\u5316\u5408\u7269\u4e0e\u786b\u8132\u7cfb\u94fe\u7684\u51e0\u4f55\u6784\u578b<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

DFT\u8ba1\u7b97\u7684Re(Bipy)(CO)3<\/sub>\u5316\u5408\u7269\u4e0e\u786b\u8132\u7cfb\u94fe\u7684\u9650\u5236\u6027\u51e0\u4f55\u4f18\u5316\u7ed3\u6784\uff0cCO2<\/sub>\u7684\u7ed3\u5408\u4ee5\u53ca\u4e0e\u786b\u8132\u6c22\u539f\u5b50\u7684\u76f8\u4e92\u4f5c\u7528\u4fc3\u8fdb\u4e86C-O\u952e\u88c2\u89e3\u3002<\/p>\n

\u56fe<\/strong>2. <\/strong>\u5316\u5408\u7269<\/strong>1<\/strong>\u5728<\/strong>N2<\/sub><\/strong>\u548c<\/strong>CO2<\/sub><\/strong>\u5b58\u5728\u4e0b\u7684<\/strong>1H NMR<\/strong>\u8c31<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

\u5728N2<\/sub>\u548cCO2<\/sub>\u5b58\u5728\u4e0b\u7532\u82ef\u4e2d1\u76841<\/sup>H NMR\u8c31\u663e\u793a\u51fa\u4e0e\u786b\u8132\u90e8\u5206\u7684\u7ed3\u5408\u3002\u5708\u51fa\u4e86\u786b\u8132\u90e8\u5206\u7684H\u539f\u5b50\u7684\u5cf0\u3002<\/p>\n

\u56fe<\/strong>3.<\/strong> \u5316\u5408\u7269<\/strong>1<\/strong>\u5728<\/strong>MeCN<\/strong>\u4e2d\u7684\u5faa\u73af\u4f0f\u5b89\u56fe<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

\u7535\u5316\u5b66\u5b9e\u9a8c\u652f\u6301\u4e86\u5728CO2<\/sub>\u8fd8\u539f\u53cd\u5e94\u4e2d\u6d89\u53ca\u4e86\u6c22\u7684\u8f6c\u79fb\u3002\uff08\u5de6\u56fe\uff091 mM\u7684\u5316\u5408\u72691\uff0c1 bar N2<\/sub>\u3002\uff08\u53f3\u56fe\uff091 mM\u7684\u5316\u5408\u72691\uff0c1 bar N2<\/sub>\uff08\u9ed1\u8272\uff09\uff1b1 mM \u7684\u5316\u5408\u72691\uff0c1 bar CO2<\/sub>\uff08\u7ea2\u8272\uff09\uff1b1 mM fac-<\/em> Re(bpy)(CO)3<\/sub>Cl\uff08\u84dd\u8272\uff09\uff0c1 bar CO2<\/sub>\u3002<\/p>\n

\u00a0<\/strong>\u56fe<\/strong>4. <\/strong>\u4e0e\u6dfb\u52a0\u8d28\u5b50\u6e90\u540e\u7684<\/strong>CV<\/strong>\u56fe\u76f8\u6bd4\uff0c<\/strong>1 mM<\/strong>\u5316\u5408\u7269<\/strong>1<\/strong>\u5728<\/strong>1 bar<\/strong>\u7684<\/strong>CO2<\/sub><\/strong>\uff08\u9ed1\u7ebf\uff09\u4e0b\u7684\u5728<\/strong>MeCN<\/strong>\u4e2d\u7684\u5faa\u73af\u4f0f\u5b89\u56fe<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

\u5de6\uff1a\u52a0\u51650.5 M PhOH\uff08\u7ea2\u8272\uff09\u3002\u53f3\uff1a\u6dfb\u52a05\uff05\u4f53\u79ef\u5206\u6570\u7684H2<\/sub>O\uff08\u7ea2\u8272\uff09\u3002<\/p>\n

\u56fe<\/strong>5. <\/strong>\u5316\u5408\u7269<\/strong>1<\/strong>\u4e2d\u7684\u6c34\uff08<\/strong>I<\/strong>\uff09\u4e0e\u8d28\u5b50<\/strong>1<\/strong>\u548c<\/strong>2<\/strong>\u53ca\u5176\u524d\u4f53\u914d\u4f53<\/strong>L1<\/strong>\uff08<\/strong>IS<\/strong>\uff09\u4e4b\u95f4\u7684\u5206\u5b50\u95f4\u540c\u6838<\/strong>NOE<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

\u56fe<\/strong>6. DFT<\/strong>\u8ba1\u7b97\u7684\u5316\u5408\u7269<\/strong>1-CO2<\/sub><\/strong>\u590d\u5408\u7269\u7684\u7a33\u5b9a\u7ed3\u6784<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

DFT\u8ba1\u7b97\u76841-CO2<\/sub>\u590d\u5408\u7269\u7684\u7a33\u5b9a\u7ed3\u6784\uff0c\u663e\u793a\u4e86\u786b\u8132\u8d28\u5b50\u7684\u201c\u8df3\u8dc3\u201d\uff0cCO2<\/sub>\u7684\u7ed3\u5408\u4ee5\u53ca\u4e0e\u786b\u8132\u6c22\u539f\u5b50\u7684\u76f8\u4e92\u4f5c\u7528\u4ee5\u4fc3\u8fdbC-O\u952e\u88c2\u89e3\u3002<\/p>\n

\u56fe<\/strong>7. <\/strong>\u5728<\/strong>0.1 M TBAPF6<\/sub>\u6eb6\u6db2\u4e2d<\/strong>\uff0c\u5316\u5408\u7269<\/strong>1<\/strong>\u5728<\/strong>CD3<\/sub>CN<\/strong>\u4e2d\u7684<\/strong>1<\/sup><\/strong>H NMR<\/strong>\u8c31<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

\u7eff\u8272\u8868\u793a\u8fd8\u539f\u524d\uff0c\u7ea2\u8272\u4e3a\u8fd8\u539f1 e–<\/sup>\uff0c\u6d45\u84dd\u8272\u4e3a\u8fd8\u539f2 e–<\/sup>\uff0c\u6df1\u84dd\u8272\u4e3a\u8fd8\u539f3 e–<\/sup>\u3002\u4ee5Ag\/AgNO3<\/sub>\u4e3a\u53c2\u6bd4\uff0c-2.0 V\u4e0b\u8fdb\u884c\u8fd8\u539f\u3002<\/p>\n

\u56fe<\/strong>8. <\/strong>\u53cc\u7535\u5b50\u548c\u4e09\u7535\u5b50\u8fd8\u539f\u7684\u5316\u5408\u7269<\/strong>1<\/strong>\u5728\u73af\u5883\u6e29\u5ea6\u4e0b\u7684<\/strong>x<\/strong>\u6ce2\u6bb5<\/strong>EPR<\/strong>\u8c31<\/strong><\/p>\n

 <\/p>\n

\"\"<\/p>\n

\u5728\u73af\u5883\u6e29\u5ea6\u4e0b\uff0c\u53cc\u7535\u5b50\uff08\u4e0a\u56fe\uff09\u548c\u4e09\u7535\u5b50\u8fd8\u539f\uff08\u4e0b\u56fe\uff09\u7684\u5316\u5408\u72691\u7684X\u6ce2\u6bb5EPR\u5149\u8c31\u3002\u4ee5Ag\/AgNO3<\/sub>\u4e3a\u53c2\u6bd4\uff0c-2.0 V\u4e0b\u8fdb\u884c\u8fd8\u539f\u3002<\/p>\n

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

\u672c\u9879\u7814\u7a76\u8868\u660e\uff0c\u5728\u7528\u4e8e\u7535\u5316\u5b66\u8fd8\u539fCO2<\/sub>\u7684\u7ecf\u5178Re(bipy)(CO)3<\/sub>X\u50ac\u5316\u5242\u7684\u4e8c\u914d\u4f4d\u5c42\u4e2d\u7684\u786b\u8132\u5728\u50ac\u5316\u5faa\u73af\u7684C-O\u952e\u88c2\u89e3\u6b65\u9aa4\u4e2d\u53d1\u6325\u4e86\u7684\u6c22\u952e\u4fc3\u8fdb\u5242\u548c\u8d28\u5b50\u4f9b\u4f53\u6d3b\u6027\u5242\u7684\u4f5c\u7528\u3002\u8fd9\u4f7f\u5f97\u4e0e\u7535\u5316\u5b66\u6d4b\u91cf\u6240\u793a\u7684Re(bipy)(CO)3<\/sub>X\u76f8\u6bd4\uff0c\u5316\u5408\u72691\u7684\u901f\u7387\u663e\u8457\u52a0\u901f\u4e861\u4e2a\u6570\u91cf\u7ea7\uff1b\u5728\u63a7\u5236\u7535\u4f4d\u7535\u89e3\u5b9e\u9a8c\u4e2d\uff0c\u5316\u5408\u72691\u572815\u5c0f\u65f6\u4fdd\u6301\u5185\u7a33\u5b9a\u3002\u901a\u8fc7\u89c2\u5bdf1<\/sup>H\u548c13<\/sup>C NMR\u8c31\u4e2d\u7684\u5316\u5b66\u4f4d\u79fb\uff0c\u53d1\u73b0\u786b\u8132\u57fa\u56e2\u4e0eCO2<\/sub>\u5f62\u6210\u4e86\u6c22\u952e\uff1b\u5e76\u4e14\u786b\u8132\u57fa\u56e2\u4e0a\u7684\u6c22\u539f\u5b50\u7684\u4e0d\u7a33\u5b9a\u6027\u5df2\u901a\u8fc71D NOE\u5b9e\u9a8c\u9a8c\u8bc1\u3002\u540c\u65f6\uff0cDFT\u8ba1\u7b97\u8868\u660e\uff0c\u4e0e\u53cc\u5421\u5576\u8d28\u5b50\u76f8\u90bb\u7684\u539f\u59cb\u201cNH\u201d\u5b8c\u5168\u9a7b\u7559\u5728\u7fa7\u9178\u76d0\u4e2d\u95f4\u4f53\u7684\u6c27\u539f\u5b50\u4e0a\uff0c\u5728\u9ad8\u80fd\u201cNH\u201d\u5f62\u5f0f\u548c\u975e\u5e38\u7a33\u5b9a\u7684\u201cOH\u201d\u7ed3\u6784\u4e4b\u95f4\u6ca1\u6709\u4efb\u4f55\u5c40\u90e8\u6781\u5c0f\u503c\u3002\u56e0\u6b64\uff0c\u786b\u8132\u90e8\u5206\u7684NH\u8d28\u5b50\u662f\u65e0\u81ea\u7531\u80fd\u5792\u7684\u6d3b\u6027\u8d28\u5b50\u4f9b\u4f53\uff1b\u5e76\u4e14\u7535\u5316\u5b66\u6d4b\u91cf\u4e5f\u652f\u6301\u4e86\u8fd9\u4e00\u7ed3\u8bba\u3002<\/p>\n

\u6587\u732e\u94fe\u63a5\uff1a<\/strong>A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO2<\/sub> and a Proton Donor Promotes the Electrochemical Reduction of CO2<\/sub> to CO Catalyzed by a Rhenium Bipyridine-Type Complex <\/strong><\/a>(Journal of the American Chemical Society 2018, DOI: 10.1021\/jacs.8b05658)<\/p>\n

\u672c\u6587\u7531\u6750\u6599\u4eba\u8ba1\u7b97\u6750\u6599\u7ec4Annay\u4f9b\u7a3f\uff0c\u6750\u6599\u725b\u6574\u7406\u7f16\u8f91\u3002<\/p>\n

\u6b22\u8fce\u5927\u5bb6\u5230\u6750\u6599\u4eba\u5ba3\u4f20\u79d1\u6280\u6210\u679c\u5e76\u5bf9\u6587\u732e\u8fdb\u884c\u6df1\u5165\u89e3\u8bfb\uff0c\u6295\u7a3f\u90ae\u7bb1tougao@cailiaoren.com<\/a>\u3002<\/p>\n

\u6295\u7a3f\u4ee5\u53ca\u5185\u5bb9\u5408\u4f5c\u53ef\u52a0\u7f16\u8f91\u5fae\u4fe1\uff1a<\/strong>cailiaokefu<\/strong>\u3002<\/strong><\/p>\n","protected":false},"excerpt":{"rendered":"

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