{"id":168444,"date":"2019-03-12T06:30:19","date_gmt":"2019-03-11T22:30:19","guid":{"rendered":"http:\/\/www.cailiaoniu.com\/?p=168444"},"modified":"2019-03-11T18:57:50","modified_gmt":"2019-03-11T10:57:50","slug":"%e3%80%90%e6%9c%aa%e6%a0%a1%e7%a8%bf%e3%80%91%e5%8d%b0%e5%ba%a6%e6%b3%b0%e7%b1%b3%e5%b0%94%e7%ba%b3%e5%be%b7%e9%82%a6%e4%b8%ad%e5%a4%ae%e5%a4%a7%e5%ad%a6j-mater-chem-a%ef%bc%9a%e9%85%8d","status":"publish","type":"post","link":"http:\/\/www.cailiaoniu.com\/?p=168444","title":{"rendered":"\u5370\u5ea6\u6cf0\u7c73\u5c14\u7eb3\u5fb7\u90a6\u4e2d\u592e\u5927\u5b66J. Mater. Chem. A\uff1a\u914d\u4f4d\u6c22\u5316\u7269\u4e2d\u7684\u6c22\uff08H+1\u548cH\u22121\uff09\u5728\u8303\u5fb7\u534e\u76f8\u4e92\u4f5c\u7528\u4e0b\u7684\u4e24\u6027\u884c\u4e3a"},"content":{"rendered":"

\u00a0<\/b><\/strong>\u3010\u5f15\u8a00\u3011<\/b><\/strong><\/p>\n

\u4e3a\u4e86\u5bfb\u627e\u6f5c\u5728\u7684\u50a8\u6c22\u6750\u6599\uff0c\u56fd\u5185\u5916\u5bf9\u9ad8\u91cd\u91cf\u3001\u9ad8\u5bb9\u91cf\u6c22\u5316\u7269\u7684\u7814\u7a76\u65e5\u76ca\u53d7\u5230\u91cd\u89c6\u3002\u6c22\u662f\u4e00\u79cd\u72ec\u7279\u7684\u5143\u7d20\uff0c\u5728\u56fa\u4f53\u4e2d\u5177\u6709\u6b63\u3001\u8d1f\u6216\u4e2d\u6027\u6c27\u5316\u6001\u3002\u5982\u679c\u80fd\u5728\u540c\u4e00\u7ed3\u6784\u6846\u67b6\u5185\u627e\u5230\u6c22\u7684\u6b63\u3001\u8d1f\u6c27\u5316\u6001\u90fd\u5b58\u5728\u7684\u50a8\u6c22\u6750\u6599\uff0c\u90a3\u4e48\u5c31\u80fd\u5bb9\u7eb3\u9ad8\u4f53\u79ef\u5bc6\u5ea6\u7684\u6c22\u3002\u56e0\u6b64\uff0c\u4ece\u6839\u672c\u4e0a\u548c\u6280\u672f\u4e0a\u6765\u8bf4\uff0c\u786e\u5b9a\u6c22\u5177\u6709\u4e24\u6027\u6027\u8d28\u7684\u5316\u5408\u7269\u5e76\u4e86\u89e3\u5176\u6765\u6e90\u7684\u5fc5\u8981\u6807\u51c6\u662f\u5f88\u91cd\u8981\u7684\u3002\u73af\u4e09\u787c\u70f7\u7684\u5b9e\u9a8c\u7ed3\u6784\u5206\u6790\u8868\u660e\uff0c\u6c22\u5728\u540c\u4e00\u7ed3\u6784\u4e2d\u5177\u6709\u9634\u79bb\u5b50\u548c\u9633\u79bb\u5b50\u884c\u4e3a\u3002\u53e6\u5916\uff0c\u5c06\u50a8\u6c22\u6750\u6599\u7528\u4e8e\u5b9e\u9645\u5ba4\u6e29\u5e94\u7528\u7684\u603b\u4f53\u8981\u6c42\u6982\u62ec\u4e3a\uff1a\u9664\u826f\u597d\u7684\u52a8\u529b\u5b66\u3001\u53ef\u9006\u6027\u548c\u89e3\u5438\u6e29\u5ea6\u7565\u9ad8\u4e8e\u5ba4\u6e29\u5916\uff0c\u50a8\u6c22\u6750\u6599\u7684\u91cd\u91cf\u5bb9\u91cf> 6\u00a0wt %\uff0c\u4f53\u79ef\u5bb9\u91cf> 50\u00a0kg m-3<\/sup>\u3002\u4e3a\u4e86\u514b\u670d\u6709\u6548\u50a8\u6c22\u7684\u6280\u672f\u9650\u5236\uff0c\u6700\u8fd1\u7684\u7814\u7a76\u96c6\u4e2d\u5728\u901a\u8fc7\u5316\u5b66\u76f8\u4e92\u4f5c\u7528\u7684\u56fa\u6001\u50a8\u5b58\uff0c\u8fd9\u662f\u4e00\u79cd\u53ef\u884c\u7684\u65b9\u6cd5\u3002\u56fa\u6001\u5b58\u50a8\u6750\u6599\u662f\u5b9e\u73b0\u6240\u9700\u91cd\u91cf\u548c\u4f53\u79ef\u5bc6\u5ea6\u7684\u552f\u4e00\u89e3\u51b3\u65b9\u6848\uff0c\u56e0\u6b64\u53d7\u5230\u4e86\u6781\u5927\u7684\u5173\u6ce8\u3002\u56fa\u6001\u5b58\u50a8\u6750\u6599\u5305\u62ec\u91d1\u5c5e\u6c22\u5316\u7269\u3001\u91d1\u5c5e\u95f4\u6c22\u5316\u7269\u3001\u914d\u4f4d\u6c22\u5316\u7269\u548c\u5316\u5b66\u6c22\u5316\u7269\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0c\u914d\u4f4d\u6c22\u5316\u7269\u5177\u6709\u826f\u597d\u7684\u50a8\u6c22\u80fd\u529b\u3001\u91cd\u91cf\u8f7b\u3001\u4f53\u79ef\u5bc6\u5ea6\u5927\u7b49\u4f18\u70b9\u3002\u4f46\u7531\u4e8e\u5176\u4e0d\u53ef\u9006\u6027\u5dee\u3001\u5206\u89e3\u6e29\u5ea6\u9ad8\u3001\u53cd\u5e94\u52a8\u529b\u5b66\u6162\uff0c\u5728\u5927\u89c4\u6a21\u5e94\u7528\u4e2d\u4ecd\u5b58\u5728\u95ee\u9898\u3002<\/p>\n

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

\u8fd1\u65e5\uff0c\u5728\u5370\u5ea6\u6cf0\u7c73\u5c14\u7eb3\u5fb7\u90a6\u4e2d\u592e\u5927\u5b66P. Ravindran\u6559\u6388<\/b><\/strong>\u56e2\u961f\uff08\u901a\u8baf\u4f5c\u8005\uff09<\/b><\/strong>\u5e26\u9886\u4e0b\uff0c\u4e0e\u632a\u5a01\u5965\u65af\u9646\u5927\u5b66<\/b><\/strong>\u5408\u4f5c\uff0c\u57fa\u4e8e(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u7684\u9ad8\u4f53\u79ef\u5bc6\u5ea6\uff0c\u88ab\u89c6\u4e3a\u6f5c\u5728\u7684\u50a8\u6c22\u6750\u6599\uff0c\u56e2\u961f\u8bbe\u60f3\u5bf9(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u4f53\u7cfb\u4e2d\u5404\u7ec4\u5206\u4e4b\u95f4\u7684\u5316\u5b66\u952e\u8fdb\u884c\u7814\u7a76\uff0c\u89e3\u91ca\u6c22\u5b58\u5728\u7684\u4e24\u6027\u72b6\u6001\u3002\u4e3a\u4e86\u7406\u89e3\u8303\u5fb7\u534e\u76f8\u4e92\u4f5c\u7528\u5bf9\u7ed3\u6784\u53c2\u6570\u7684\u5f71\u54cd\uff0c\u56e2\u961f\u8003\u8651\u4e8612\u79cd\u4e0d\u540c\u7684vdW\u4fee\u6b63\u6cdb\u51fd\uff0c\u53d1\u73b0optPBE-vdW\u51fd\u6570\u53ef\u9760\u5730\u9884\u6d4b\u5e73\u8861\u7ed3\u6784\u53c2\u6570\uff0c\u8bef\u5dee\u5c0f\u4e8e0.009%\u3002\u56e0\u6b64\uff0c\u5229\u7528optPBE-vdW\u51fd\u6570\u8ba1\u7b97\u7535\u8377\u5bc6\u5ea6\u3001\u7535\u5b50\u5c40\u57df\u51fd\u6570\u3001\u603b\u6001\u5bc6\u5ea6\u548c\u5206\u6001\u5bc6\u5ea6\u3001Bader\u548cBorn\u6709\u6548\u7535\u8377\u7b49\u3002\u89c2\u5bdf\u5230\uff0c\u6c22\u5728\u5e26\u8d1f\u7535\u8377\u7684\u72b6\u6001\u4e0b\uff0cH\u66f4\u63a5\u8fd1B\uff0c\u800c\u5728\u5e26\u6b63\u7535\u8377\u7684\u72b6\u6001\u4e0b\uff0cH\u66f4\u63a5\u8fd1N\u65f6\uff0c\u8868\u73b0\u51fa\u4e24\u6027\u884c\u4e3a\u3002\u76f8\u5173\u6210\u679c\u4ee5\u9898\u4e3a\u201c<\/b><\/strong>Amphoteric behavior of hydrogen (H<\/b><\/strong>+1<\/b><\/sup><\/strong>\u00a0and H<\/b><\/strong>\u22121<\/b><\/sup><\/strong>) in complex hydrides from van der Waals interaction-including ab initio calculations<\/b><\/strong>\u201d<\/b><\/strong>\u53d1\u8868\u5728\u4e86J. Mater. Chem. A<\/b><\/strong>\u4e0a\u3002<\/p>\n

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

\u56fe1<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH<\/b><\/strong>2<\/b><\/sub><\/strong>)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)\u7684\u6676\u4f53\u7ed3\u6784<\/b><\/strong>\"\"<\/b><\/strong><\/p>\n

\uff08a,b\uff09\u5206\u522b\u4e3a(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u7684\u6676\u4f53\u7ed3\u6784\u3002\u6b63\u6c27\u5316\u6001\u548c\u8d1f\u6c27\u5316\u6001\u7684\u6c22\u5206\u522b\u7528\u7ea2\u8272\u548c\u7eff\u8272\u8868\u793a\u3002\u952e\u957f\u4ee5\u00c5\u8868\u793a\u3002<\/p>\n

\u00a0<\/b><\/strong>\u56fe2<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH2)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)\u7684\u603b\u80fd\u91cf\u4e0e\u4f53\u79ef\u66f2\u7ebf<\/b><\/strong>\"\"<\/p>\n

\u56fe<\/b><\/strong>3<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH2)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)<\/b><\/strong>\u7406\u8bba\u8ba1\u7b97\u51fa<\/b><\/strong>\u7684<\/b><\/strong>\u603b\u6001<\/b><\/strong>\u5bc6\u5ea6<\/b><\/strong>\"\"<\/p>\n

\u57fa\u4e8eGGA\u548coptPBE-vdW\u6cdb\u51fd\u8ba1\u7b97(BH2<\/sub>NH2)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u5f97\u5230\u7684\u603b\u6001\u5bc6\u5ea6\uff08TDOS\uff09\u3002\u5b9e\u7ebf\uff08\u7ea2\u8272\uff09\u548c\u865a\u7ebf\uff08\u9752\u8272\uff09\u66f2\u7ebf\u8868\u793a\u4eceoptPBE-vdW\u548cGGA\u8ba1\u7b97\u83b7\u5f97\u7684TDOS\u3002<\/p>\n

\u56fe<\/b><\/strong>4<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH2)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)<\/b><\/strong>\u7406\u8bba\u8ba1\u7b97\u51fa<\/b><\/strong>\u7684<\/b><\/strong>\u5206\u6001\u5bc6\u5ea6<\/b><\/strong>\"\"<\/p>\n

(BH2<\/sub>NH2)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u7684\u5206\u6001\u5bc6\u5ea6\u5206\u522b\u7531\u5e73\u8861\u4f53\u79ef\u4e0b\u7684optPBE-vdW\u51fd\u6570\u8ba1\u7b97\u5f97\u51fa\u7684\u3002<\/p>\n

\u56fe<\/b><\/strong>5<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH<\/b><\/strong>2<\/b><\/sub><\/strong>)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)<\/b><\/strong>\u7406\u8bba<\/b><\/strong>\u8ba1\u7b97\u51fa\u7684\u4ef7\u7535\u5b50\u5bc6\u5ea6\u5206\u5e03<\/b><\/strong>\"\"<\/p>\n

(a) (BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(b) (NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u4e2d\u8ba1\u7b97\u51fa\u7684\u4ef7\u7535\u5b50\u5bc6\u5ea6\u5206\u5e03\u3002\u7535\u5b50\u5bc6\u5ea6\uff08\u5355\u4f4d\u4e3ae\/\u00c53<\/sup>\uff09\u88ab\u6295\u5f71\u5230\u4e00\u4e2a\u5e73\u9762\u4e0a\uff0c\u8fd9\u4e2a\u5e73\u9762\u4e0a\u6709B-H\u548cN-H\u952e\u3002<\/p>\n

\u56fe<\/b><\/strong>6<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH<\/b><\/strong>2<\/b><\/sub><\/strong>)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)\u8ba1\u7b97\u7684\u7535\u5b50\u5c40\u57df\u51fd\u6570\uff08ELF\uff09<\/b><\/strong>\"\"<\/p>\n

(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u7684\u7535\u5b50\u5c40\u57df\u51fd\u6570\uff08ELF\uff09\u4e3aoptPBE-vdW\u51fd\u6570\u8ba1\u7b97\u5f97\u5230\u7684\u3002\u5728B-H\u548cN-H\u952e\u7684\u5e73\u9762\u4e0a\u663e\u793a\u4e86ELF\u5206\u5e03\u3002<\/p>\n

\u56fe<\/b><\/strong>7<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH<\/b><\/strong>2<\/b><\/sub><\/strong>)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)\u4ef7\u7535\u5b50<\/b><\/strong>\u5c40\u57df<\/b><\/strong>\u51fd\u6570\u7684\u7b49\u503c\u9762<\/b><\/strong>\"\"<\/p>\n

(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u4ef7\u7535\u5b50\u5c40\u57df\u51fd\u6570\u7684\u7b49\u503c\u9762\uff08\u503c0.97\uff09\u3002<\/p>\n

\u56fe<\/b><\/strong>8<\/b><\/strong>\u00a0<\/b><\/strong>(BH<\/b><\/strong>2<\/b><\/sub><\/strong>NH<\/b><\/strong>2<\/b><\/sub><\/strong>)<\/b><\/strong>3<\/b><\/sub><\/strong>\u548c(NH<\/b><\/strong>4<\/b><\/sub><\/strong>)<\/b><\/strong>2<\/b><\/sub><\/strong>(B<\/b><\/strong>12<\/b><\/sub><\/strong>H<\/b><\/strong>12<\/b><\/sub><\/strong>)\u7ec4\u5206\u95f4\u7684COHP<\/b><\/strong>\u5206\u6790<\/b><\/strong>\"\"<\/p>\n

\u901a\u8fc7optPBE-vdW\u51fd\u6570\u5f97\u5230\u7684(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4<\/sub>)2<\/sub>(B12<\/sub>H12<\/sub>)\u7ec4\u5206\u95f4\u7684COHP\u3002<\/p>\n

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

\u5229\u7528ab initio\u80fd\u5e26\u7ed3\u6784\u65b9\u6cd5\uff0c\u56e2\u961f\u5206\u6790\u4e86(BH2<\/sub>NH2<\/sub>)3<\/sub>\u548c(NH4)2<\/sub>(B12<\/sub>H12<\/sub>)\u4e2d\u5404\u7ec4\u5206\u4e4b\u95f4\u7684\u5316\u5b66\u952e\u3002\u56e2\u961f\u8bc1\u660e\u4e86\uff0c\u5728\u76f8\u540c\u7684\u7ed3\u6784\u6846\u67b6\u4e0b\uff0c\u6c22\u50a8\u5b58\u7cfb\u7edf\u53ef\u4ee5\u6709\u5e26\u6b63\u7535\u548c\u8d1f\u7535\u7684\u6c22\u3002\u5982\u679c\u5b58\u5728\u5f7c\u6b64\u76f8\u90bb\u7684\u5e26\u6b63\u7535\u548c\u5e26\u8d1f\u7535\u7684\u6c22\u79bb\u5b50\uff0c\u7531\u4e8e\u5b83\u4eec\u4e4b\u95f4\u7684\u5e93\u4ed1\u5f15\u529b\u800c\u653e\u7f6e\u5f97\u66f4\u8fd1\uff0c\u4ece\u800c\u63d0\u9ad8\u4e86\u4f53\u79ef\u50a8\u6c22\u80fd\u529b\u3002\u56e2\u961f\u5e0c\u671b\u901a\u8fc7\u5bf9\u5177\u6709\u4e24\u6027\u884c\u4e3a\u548c\u9ad8\u5bb9\u91cf\u7684\u5b9e\u9645\u50a8\u6c22\u6750\u6599\u7684\u7814\u7a76\uff0c\u63a8\u52a8\u8fd9\u4e00\u65b9\u5411\u7684\u8fdb\u4e00\u6b65\u7814\u7a76\u3002<\/p>\n

\u6587\u732e\u94fe\u63a5\uff1a<\/b><\/strong>Amphoteric behavior of hydrogen (H<\/u>+1<\/sup><\/u>\u00a0and H<\/u>\u22121<\/sup><\/u>) in complex hydrides from van der Waals interaction-including ab initio calculations<\/u><\/a>\uff08J. Mater. Chem. A, 2019, DOI:10.1039\/C8TA11685G\uff09<\/p>\n

\u672c\u6587\u7531\u6750\u6599\u4eba\u7f16\u8f91\u90e8\u5b66\u672f\u7ec4\u6728\u6587\u97ec<\/b><\/strong>\u7ffb\u8bd1\uff0c\u6750\u6599\u725b\u6574\u7406\u7f16\u8f91\u3002<\/p>\n

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