{"id":241947,"date":"2022-09-12T06:35:26","date_gmt":"2022-09-11T22:35:26","guid":{"rendered":"http:\/\/www.cailiaoniu.com\/?p=241947"},"modified":"2022-09-11T00:19:18","modified_gmt":"2022-09-10T16:19:18","slug":"nature-%e7%be%8e%e5%9b%bd%e5%8a%a0%e5%b7%9e%e7%90%86%e5%b7%a5jonas-c-peters%ef%bc%9a%e9%80%9a%e8%bf%87%e8%b4%a8%e5%ad%90%e8%80%a6%e5%90%88%e7%94%b5%e5%ad%90%e8%bd%ac%e7%a7%bb%e7%9a%84%e4%b8%b2","status":"publish","type":"post","link":"http:\/\/www.cailiaoniu.com\/?p=241947","title":{"rendered":"Nature\/\u7f8e\u56fd\u52a0\u5dde\u7406\u5de5Jonas C. Peters\uff1a\u901a\u8fc7\u8d28\u5b50\u8026\u5408\u7535\u5b50\u8f6c\u79fb\u7684\u4e32\u8054\u7535\u50ac\u5316 \u56fa\u6c2e"},"content":{"rendered":"

\u4e00\u3001\u3010\u5bfc\u8bfb\u3011<\/strong><\/p>\n

\u65b0\u7684\u7535\u5316\u5b66\u6c28 (NH3<\/sub>) \u5408\u6210\u6280\u672f\u4f5c\u4e3a\u54c8\u4f2f-\u535a\u4e16\uff08Haber-Bosch\uff09\u5206\u5e03\u5f0f\u80a5\u6599\u751f\u4ea7\u5de5\u827a\u7684\u8865\u5145\u8def\u7ebf\uff0c\u901a\u8fc7\u53ef\u518d\u751f\u80fd\u6e90\u53d1\u7535\u5c06\u6c28\u4f5c\u4e3a\u96f6\u78b3\u71c3\u6599\u800c\u5907\u53d7\u5173\u6ce8\u3002<\/p>\n

\u7531\u6b64\uff0c\u5927\u91cf\u9488\u5bf9\u975e\u5747\u76f8\u6750\u6599\u4f5c\u4e3a\u6c2e\u8fd8\u539f\u53cd\u5e94 (N2<\/sub>RR)\u7684\u7535\u50ac\u5316\u5242\u7684\u57fa\u7840\u7814\u7a76\u51fa\u73b0\u3002\u4f46\u8fd9\u4e9b\u4f53\u7cfb\u666e\u904d\u5177\u6709\u7a33\u5b9a\u6027\u8f83\u5dee\u3001NH3\u9009\u62e9\u6027\u5dee\u7684\u95ee\u9898\uff0c\u4e5f\u5c31\u662f\u6790\u6c22\u53cd\u5e94 (HER) \u4f18\u4e8e N2<\/sub>RR\u3002\u867d\u7136\u5206\u5b50\u50ac\u5316\u5242\u4f53\u7cfb\u53ef\u4ee5\u8fdb\u884c\u7cbe\u7ec6\u7684\u8c03\u6574\u4ee5\u6ee1\u8db3N2<\/sub>\u7ed3\u5408\u548c\u6fc0\u6d3b\u7684\u7535\u5b50\u8981\u6c42\uff0c\u5e76\u63d0\u4f9b\u66ff\u4ee3\u7b56\u7565\uff0c\u4f46\u540c\u6837\u7684\u9009\u62e9\u6027\u95ee\u9898\u963b\u788d\u4e86\u8fdb\u5c55\u2014\u2014HER\u4ecd\u5360\u4e3b\u5bfc\u5730\u4f4d\u3002<\/p>\n

\u4e8c\u3001\u3010\u6210\u679c\u63a0\u5f71\u3011<\/strong><\/p>\n

\u8fd1\u65e5\uff0c\u6765\u81ea\u7f8e\u56fd\u52a0\u5dde\u7406\u5de5\u5b66\u9662\u7684Jonas C. Peters\u7b49\u4eba\u53d1\u8868\u4e86\u4e00\u79cd\u4e32\u8054\u50ac\u5316\u7b56\u7565\uff0c\u4e3a\u8fd9\u4e2a\u96be\u9898\u63d0\u4f9b\u4e86\u89e3\u51b3\u65b9\u6848\uff1a\u4e00\u79cd\u53ef\u4ee5\u4ecb\u5bfc N2<\/sub> \u8fd8\u539f\u5faa\u73af\u7684\u5206\u5b50\u7edc\u5408\u7269\u4e0e\u8f85\u52a9\u50ac\u5316\u5242\u914d\u5408\u4f7f\u7528\uff0c\u8f85\u52a9\u50ac\u5316\u5242\u8fde\u63a5\u7535\u6781\u548c\u9178\uff0c\u4ee5\u4ecb\u5bfc\u8d28\u5b50\u8026\u5408\u7684\u7535\u5b50\u8f6c\u79fb\u6b65\u9aa4\uff0c\u4ece\u800c\u5728\u6709\u5229\u7684\u65bd\u52a0\u7535\u4f4d\uff08\u22121.2 V vs Fc+\/0<\/sup>\uff09\u548c\u6574\u4f53\u70ed\u529b\u5b66\u6548\u7387\u4e0b\u4fc3\u8fdbN-H\u952e\u7684\u5f62\u6210\u3002N2<\/sub>RR \u5faa\u73af\u7684\u67d0\u4e9b\u4e2d\u95f4\u4f53\u5c06\u901a\u8fc7\u975e\u8026\u5408\u7535\u5b50\u8f6c\u79fb\u6216\u8d28\u5b50\u8f6c\u79fb\u6b65\u9aa4\u800c\u4e0d\u53d1\u751f\u53cd\u5e94\u3002\u7ed3\u6784\u4e0d\u540c\u7684\u51e0\u79cd\u91d1\u5c5e\uff08W\u3001Mo\u3001Os\u3001Fe\uff09\u7684\u914d\u5408\u7269\u4e5f\u5728\u4ecb\u4f53\u5b58\u5728\u7684\u60c5\u51b5\u4e0b\u4ee5\u76f8\u540c\u7684\u7535\u4f4d\u4ecb\u5bfc N2<\/sub>RR \u7535\u50ac\u5316\uff0c\u8fd9\u8868\u660e\u4e86\u8fd9\u79cd\u4e32\u8054\u65b9\u6cd5\u7684\u666e\u904d\u6027\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u4ee5\u201cTandem electrocatalytic N2<\/sub> fixation via proton-coupled electron transfer<\/strong>\u201d\u4e3a\u9898\u53d1\u8868\u5728Nature<\/em><\/strong>\u4e0a\u3002<\/p>\n

\"\"<\/p>\n

\u4e09\u3001\u3010\u6838\u5fc3\u521b\u65b0\u70b9\u3011<\/strong><\/p>\n

\u91c7\u7528\u8d28\u5b50\u8026\u5408\u7535\u5b50\u8f6c\u79fb(PCET)\u4ecb\u8d28\u7684\u4e32\u8054\u7535\u50ac\u5316\u7b56\u7565\uff0c\u963b\u6b62\u4e86\u50ac\u5316\u540e\u7684\u6790\u6c22\u53cd\u5e94\u53d1\u751f\u3002<\/p>\n

\u56db\u3001\u3010\u6570\u636e\u6982\u89c8\u3011<\/strong><\/p>\n

\"\"<\/p>\n

\u56fe1<\/strong> N2<\/sub>RR \u7535\u50ac\u5316\u7814\u7a76\u8fdb\u5c55 \u00a9 2022 Springer Nature<\/p>\n

a\uff0c\u7528\u4e8e\u50ac\u5316N2<\/sub>\u5230NH3<\/sub>\u8f6c\u5316\u7684\u4ee3\u8868\u6027\u8fdc\u7aef\u5faa\u73af\u3002b\uff0c\u5148\u524d\u62a5\u9053\u7684\u4e00\u79cd\u57fa\u4e8e\u4e09\uff08\u81a6\uff09\u787c\u70f7Fe\u4f53\u7cfb\u7684\u5206\u5b50N2<\/sub>RR\u7535\u50ac\u5316\u5242\uff0c\u5728-35\u2103\u7684\u6e29\u5ea6\u4e0b\u5728\u73bb\u78b3\u7535\u6781\u4e0a\u4ee5-2.1 V\u7684\u7535\u538b\u5de5\u4f5c\u3002c\uff0cPickett\u7684\u65e9\u671f\u5de5\u4f5c\u5c55\u793a\u4e86\u4f7f\u7528\u5206\u5b50\u7edc\u5408\u7269W(N2<\/sub>)2<\/sub>\u5728-2.6 V\u7684\u65bd\u52a0\u7535\u4f4d\u4e0b\u3001\u4f7f\u7528TsOH\u7684Hg\u6c60\u7535\u6781\u4e0a\u7535\u5408\u6210NH3<\/sub>\u3002d\uff0c\u672c\u5de5\u4f5c\u4e2d\u63cf\u8ff0\u7684\u4e32\u8054\u50ac\u5316\uff0c\u57fa\u4e8e\u5c06PCET\u4ecb\u8d28Co(II,NH)+<\/sup>\u4e0e\u5206\u5b50N2<\/sub>RR\u50ac\u5316\u5242\u5076\u8054\uff0c\u5728\u76f8\u5bf9\u6e29\u548c\u7684\u7535\u4f4d\uff08-1.2 V\uff0c\u4f7f\u7528TsOH\uff09\u4e0b\u5b9e\u73b0\u660e\u786e\u7684\u7535\u50ac\u5316\u3002<\/p>\n

\"\"<\/p>\n

\u56fe2<\/strong> \u4e32\u8054\u50ac\u5316\u7684\u7535\u50ac\u5316N2<\/sub>RR\u3002 \u00a9 2022 Springer Nature<\/p>\n

a\uff0c\u5728\u542b\u67090.05 mM Co(III,N)+\u30010.05 mM W(N2<\/sub>)2<\/sub>\u548c5 mM TsOH\u76840.1 M [Li][NTf2<\/sub>] DME\u6eb6\u6db2\u4e2d\uff0cCPC\u4e0a\u7684\u7535\u50ac\u5316N2<\/sub>RR\uff0c\u65bd\u52a0\u7535\u4f4d-1.35 V vs Fc+\/0<\/sup>\uff0c\u4f7f\u7528BDD\u677f\u5de5\u4f5c\u7535\u6781\u3002b\uff0c\u63cf\u8ff0\u7684CPC\u5b9e\u9a8c\u7684\u7535\u6d41 (j) \u66f2\u7ebf\uff08\u9ed1\u8272\u8ff9\u7ebf\uff09\u548c\u5728\u6ca1\u6709Co(III,N)+\u4ecb\u4f53\u7684\u7c7b\u4f3cCPC\u5b9e\u9a8c\u3002c\uff0c\u4f7f\u752814<\/sup>N2<\/sub>\u300115<\/sup>N2<\/sub>\u6216\u6c29\u6c14\u6c14\u6c1b\u901a\u8fc71H NMR\u5149\u8c31\u5728CPC\u540e\u5bf9NH3<\/sub>\u8fdb\u884c\u5b9a\u91cf\u3002W(N2<\/sub>)2<\/sub>\u7684\u5e73\u5747\u7ed3\u679c\u53ca\u5176\u76f8\u5173\u8bef\u5dee\uff08\u6807\u51c6\u504f\u5dee\uff09\u5bf9\u5e94\u4e8e\u4e09\u4e2a\u7535\u50ac\u5316\u8fd0\u884c\u3002<\/p>\n

\"\"<\/p>\n

\u56fe3<\/strong>\u4e32\u8054PCET N2<\/sub>RR\u7684\u673a\u7406\u7814\u7a76\u3002 \u00a9 2022 Springer Nature<\/p>\n

a\uff0cCV\u66f2\u7ebf\uff1a50 mM TsOH\uff08\u7070\u8272\u865a\u7ebf\uff09\uff1b0.5 mM Co(III,N)+<\/sup> \u548c50 mM TsOH\uff08\u9ed1\u8272\uff09\uff1b0.5 mM (TsO)W(NNH2<\/sub>)+<\/sup>\uff08\u7eaf\u7ea2\u8272\uff09\uff1b0.5 mM (TsO)W(NNH2<\/sub>)+<\/sup>\u548c50 mM TsOH\uff08\u7ea2\u8272\u865a\u7ebf\uff09\uff1b0.5 mM Co(III,N)+<\/sup>\/(TsO)W(NNH2<\/sub>)+<\/sup>\u548c50 mM TsOH\uff08\u7d2b\u8272\uff09\u3002b\uff0cCV\u66f2\u7ebf\uff1a0.5 mM Co(III,NH)2+<\/sup>\/(TsO)W(NNH2<\/sub>)+<\/sup>\uff08\u7d2b\u8272\u8ff9\u7ebf\uff09\u4e0e 0.5 mM Co(III,NH)2+<\/sup>\uff08\u7ea2\u8272\u8ff9\u7ebf\uff09\u548c0.5 mM Co(III,N)+\uff08\u84dd\u8272\u8ff9\u7ebf\uff09\u57285 mV s-1<\/sup>\u4e0b\u7684\u5bf9\u6bd4\u3002c\uff0c0.5 mM (TsO)W(NNH2<\/sub>)+<\/sup>\u5728THF \u4e2d\u4e0e2 equiv\u7684\u5316\u5b66\u53cd\u5e94\u3002\u5728\u8fc7\u91cf\u9178\u5b58\u5728\u4e0b\u7684THF\u4e2d\uff0cCo(II,N) \u548c\u76f8\u5e94\u768431<\/sup>P NMR \u5149\u8c31\u3002 d\uff0cCV\u66f2\u7ebf\uff1a0.5 mM (N3<\/sub>)W(N)\uff08\u9ed1\u8272\uff09\uff1b0.5 mM (N3<\/sub>)W(N)\u548c1 equiv. TsOH\uff08\u7eaf\u7ea2\u8272\uff09\uff1b0.5 mM (N3<\/sub>)W(N)\u548c50 mM TsOH\uff08\u7ea2\u8272\u865a\u7ebf\uff09\uff1b0.5 mM Co(III,N)+<\/sup>\/(N3<\/sub>)W(N)\u548c50 mM TsOH\uff08\u7d2b\u8272\uff09\u3002e\uff0c\u50ac\u5316\u7535\u6d41 (icat<\/sub>) \u4e0e\u4e0d\u540c\u8f85\u52a9\u50ac\u5316\u5242\u6d53\u5ea6\u7684\u5173\u7cfb\u56fe\u3002f\uff0c\u5728\u6807\u51c6\u7535\u50ac\u5316\u6761\u4ef6\u4e0b\uff0c\u5728 Co(III,N)+<\/sup>\u548c TsOH \u5b58\u5728\u4e0b\u7814\u7a76\u7684\u51e0\u79cd\u4ee3\u8868\u6027M(N2<\/sub>) \u50ac\u5316\u5242\u7684CV\u66f2\u7ebf\uff08\u5176\u5316\u5b66\u7ed3\u6784\u89c1\u56fe4a\uff09\uff0c\u53ef\u4ee5\u770b\u51faN2<\/sub>RR\u7684\u591a\u7535\u5b50\u50ac\u5316\u6ce2\u6bcf\u79cd\u60c5\u51b5\u90fd\u91c7\u7528\u4e0eW(N2<\/sub>)2<\/sub>\u76f8\u540c\u7684\u504f\u7f6e\u3002\u8bf7\u6ce8\u610f\uff0ca-f\u4e2d\u7684\u6240\u6709CV\u66f2\u7ebf\u5747\u5728100 mV s-1<\/sup>\uff08\u9664\u975e\u53e6\u6709\u8bf4\u660e\uff09\u4e0b\uff0c\u4e8e0.1 M [Li][NTf2<\/sub>] THF \u6eb6\u6db2\u4e2d\u4f7f\u7528 BDD \u5706\u76d8\u4f5c\u4e3a\u5de5\u4f5c\u7535\u6781\u3001Pt \u5706\u76d8\u4f5c\u4e3a\u5bf9\u7535\u6781\u4ee5\u53caAg\/ AgOTf (5 mM) \u4f5c\u4e3a\u53c2\u6bd4\u7535\u6781\u3002eN2<\/sub>RR\uff0c\u7535\u50ac\u5316N2<\/sub>RR \u3002<\/p>\n

\"\"<\/p>\n

\u56fe4 <\/strong>\u5df2\u62a5\u9053\u7684N2<\/sub>RR\u7684\u7535\u50ac\u5316\u7814\u7a76\u3002 \u00a9 2022 Springer Nature<\/p>\n

a\uff0c\u5728\u7535\u50ac\u5316\u6761\u4ef6\u4e0b\u4e0ePCET\u4ecb\u4f53\u7ed3\u5408\u63a2\u7d22\u7684\u5206\u5b50N2<\/sub>RR \u50ac\u5316\u5242\u3002b\uff0c\u5728\u542b\u67090.05 mM Co(III,N)+<\/sup>\u30010.05 mM N2<\/sub>RR\u50ac\u5316\u5242\u548c5 mM TsOH\u76840.1 M [Li][NTf2<\/sub>] DME\u6eb6\u6db2\u4e2d\uff0cCPC\u4e0a\u6bcf\u79cd\u5206\u5b50\u50ac\u5316\u5242\u5728-1.35 V\u4e0eFc+\/0<\/sup>\u6761\u4ef6\u4e0b\u7684\u7535\u50ac\u5316\u5b9e\u9a8c\u7ed3\u679c\uff0c\u4f7f\u7528\u7684\u5de5\u4f5c\u7535\u6781\u4e3aBDD\u677f\u3002W(N2<\/sub>)2<\/sup>\u7684\u5e73\u5747\u7ed3\u679c\u53ca\u5176\u76f8\u5173\u8bef\u5dee\uff08\u6807\u51c6\u504f\u5dee\uff09\u5bf9\u5e94\u4e09\u4e2a\u7535\u50ac\u5316\u8fd0\u884c\u3002*\u4f7f\u7528GC\u6ce1\u6cab\u4f5c\u4e3a\u5de5\u4f5c\u7535\u6781\uff0c\u8f85\u52a9\u50ac\u5316\u5242\u548c1 mM TsOH \u7684\u7528\u91cf\u5747\u4e3a0.01 mM\u3002c\uff0cN2<\/sub>RR \u7684\u4f30\u8ba1\u8fc7\u7535\u52bf (\u0394\u0394Gf)\uff0c\u5305\u62ec\u6b64\u5904\u62a5\u9053\u7684\u4e32\u8054PCET\u4f53\u7cfb\u3001\u56fa\u6c2e\u9176\u3001\u4f7f\u7528EtOH\u4f5c\u4e3aH+<\/sup>\u6e90\u7684Li\u4ecb\u5bfc\u7684N2<\/sub>RR\u4ee5\u53ca\u5316\u5b66\u9a71\u52a8\u7684N2<\/sub>RR\u4e2d\u4f7f\u7528\u7684\u5404\u79cd\u8fd8\u539f\u5242\u548c\u9178\u6e90\u3002<\/p>\n

 <\/p>\n

\u4e94\u3001\u3010\u6210\u679c\u542f\u793a\u3011<\/strong><\/p>\n

\u672c\u7814\u7a76\u91c7\u7528\u53cc\u7ec4\u4efd\u4e32\u8054\u50ac\u5316\u7b56\u7565\uff0c\u914d\u5bf9\u4e00\u79cd\u5019\u9009\u5206\u5b50\u50ac\u5316\u5242<\/strong>\uff0c\u8be5\u50ac\u5316\u5242\u53ef\u4ee5\u7ed3\u5408N2<\/sub>(M-N2<\/sub>)\uff0c\u5e76\u901a\u8fc7\u5404\u79cdM-Nx<\/sub>Hy<\/sub>\u4e2d\u95f4\u4f53\uff08\u4f8b\u5982\uff0cM-N=NH, M=NNH2<\/sub>, M=NH\uff09\u4fc3\u8fdb\u5176\u591a\u6b65\u8fd8\u539f\u4e3aNH3<\/sub>\u3002\u671f\u95f4N2<\/sub>RR\u5faa\u73af\u7684\u67d0\u4e9b\u4e2d\u95f4\u4ea7\u7269\u96be\u4ee5\u901a\u8fc7\u5faa\u73af\u7684\u95ee\u9898\uff0c\u5219\u7528PCET\u6b65\u9aa4<\/strong>\u5c06\u7535\u6781\u548c\u9178\u4e0eN2<\/sub>\u8fd8\u539f\u5faa\u73af\u8fde\u63a5\u8d77\u6765\uff0c\u4ee5\u6b64\u901a\u8fc7\u975e\u5076\u8054\u7684\u7535\u5b50\u8f6c\u79fb\u6216\u8d28\u5b50\u8f6c\u79fb\u6b65\u9aa4\u6765\u89e3\u51b3\u3002\u540c\u65f6\uff0c\u51e0\u79cd\u4e0d\u540c\u7ed3\u6784\u7684\u91d1\u5c5e(W, Mo, Os, Fe)\u914d\u5408\u7269\uff0c\u4e5f\u53ef\u4ee5\u5728\u76f8\u540c\u7684\u7535\u4f4d(-1.2 V\u5bf9Fc+\/0<\/sup>) \u4e2d\u4ecb\u5bfcN2<\/sub>RR\u7535\u50ac\u5316\uff0c\u8fd9\u8868\u660e\u4e86\u8fd9\u79cd\u4e32\u8054\u65b9\u6cd5\u7684\u666e\u904d\u6027\u3002<\/p>\n

\u539f\u6587\u8be6\u60c5<\/strong>\uff1aTandem electrocatalytic N2<\/sub> fixation via proton-coupled electron transfer. Nature<\/em>. 609, 71\u201376 (2022), https:\/\/doi.org\/10.1038\/s41586-022-05011-6<\/a><\/p>\n","protected":false},"excerpt":{"rendered":"

\u4e00\u3001\u3010\u5bfc\u8bfb\u3011 \u65b0\u7684\u7535\u5316\u5b66\u6c28 (NH3) \u5408\u6210\u6280\u672f\u4f5c\u4e3a\u54c8\u4f2f-\u535a\u4e16\uff08Haber-Bosch\uff09\u5206\u5e03\u5f0f\u80a5\u6599\u751f\u4ea7\u5de5\u827a\u7684\u8865\u5145\u8def\u7ebf\uff0c\u901a\u8fc7\u53ef\u518d\u751f\u80fd\u6e90\u53d1\u7535\u5c06\u6c28\u4f5c\u4e3a\u96f6\u78b3\u71c3\u6599\u800c\u5907\u53d7\u5173…<\/p>\n","protected":false},"author":39059,"featured_media":0,"comment_status":"open","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[215,2],"tags":[293,3530,2459],"class_list":["post-241947","post","type-post","status-publish","format-standard","hentry","category-jiedu","category-keji","tag-nature","tag-3530","tag-2459"],"_links":{"self":[{"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts\/241947"}],"collection":[{"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/users\/39059"}],"replies":[{"embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=241947"}],"version-history":[{"count":4,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts\/241947\/revisions"}],"predecessor-version":[{"id":242098,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts\/241947\/revisions\/242098"}],"wp:attachment":[{"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=241947"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=241947"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=241947"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}