{"id":262355,"date":"2024-09-03T06:23:22","date_gmt":"2024-09-02T22:23:22","guid":{"rendered":"http:\/\/www.cailiaoniu.com\/?p=262355"},"modified":"2024-09-02T19:35:40","modified_gmt":"2024-09-02T11:35:40","slug":"jacs%ef%bc%9a%e9%85%b8%e6%80%a7%e7%94%b5%e8%a7%a3%e6%b6%b2%e4%b8%ad%e6%9c%89%e6%95%88%e7%94%b5%e5%82%ac%e5%8c%96co2%e8%bf%98%e5%8e%9f%ef%bc%9a%e5%85%89%e8%b0%b1%e6%b5%8b%e8%af%95%e6%89%8b%e6%ae%b5","status":"publish","type":"post","link":"http:\/\/www.cailiaoniu.com\/?p=262355","title":{"rendered":"JACS\uff1a\u9178\u6027\u7535\u89e3\u6db2\u4e2d\u6709\u6548\u7535\u50ac\u5316CO2\u8fd8\u539f\uff1a\u5149\u8c31\u6d4b\u8bd5\u624b\u6bb5\u8bc1\u5b9e\u5c40\u90e8pH\u68af\u5ea6\u4f5c\u7528"},"content":{"rendered":"

\u7b2c\u4e00\u4f5c\u8005\uff1aMadeline H. Hicks<\/strong> \u548c Dr. Weixuan Nie<\/strong> (\u8042\u4f1f\u8f69 \u535a\u58eb<\/strong>\uff0c\u73b0\u4e3a\u897f\u6e56\u5927\u5b66\u5de5\u5b66\u9662PI\/\u535a\u58eb\u751f\u5bfc\u5e08\uff0c\u6587\u672b\u9644\u6709\u4f5c\u8005\u4ecb\u7ecd<\/strong>)<\/p>\n

\u901a\u8baf\u4f5c\u8005\uff1aHarry A. Atwater, Theodor Agapie \u548c Jonas C. Peters<\/p>\n

\u901a\u8baf\u5355\u4f4d\uff1aCaltech\u00a0 \u52a0\u5dde\u7406\u5de5\u5b66\u9662<\/p>\n

\u8bba\u6587DOI\uff1ahttps:\/\/doi.org\/10.1021\/jacs.4c09512<\/a><\/p>\n

\"\"<\/p>\n

\"\"<\/p>\n

\u3010\u7814\u7a76\u80cc\u666f\u3011<\/u><\/strong><\/p>\n

\u5229\u7528\u7eff\u8272\u7535\u80fd\u5c06CO2<\/sub>\u50ac\u5316\u8fd8\u539f\uff08CO2<\/sub>R\uff09\u6210\u9ad8\u9644\u52a0\u503c\u7684\u5316\u5b66\u4ea7\u7269\u6216\u662f\u80fd\u6e90\u71c3\u6599\uff0c\u88ab\u8ba4\u4e3a\u662f\u5b9e\u73b0\u6709\u6548\u78b3\u5faa\u73af\u7684\u4e00\u79cd\u5177\u6709\u524d\u666f\u7684\u6280\u672f\u624b\u6bb5\u3002\u4f46\u662f\u73b0\u9636\u6bb5\u7edd\u5927\u591a\u6570\u7684CO2<\/sub>R\u90fd\u4f9d\u8d56\u4e8e\u4e2d\u6027\u6216\u78b1\u6027\u7535\u89e3\u6db2\u73af\u5883\u3002\u7531\u4e8eCO2<\/sub>\u5728\u4e2d\/\u78b1\u6027\u6761\u4ef6\u4e0b\u4f1a\u53cd\u5e94\u751f\u6210\u78b3\u9178\u6839\u6216\u78b3\u9178\u6c22\u6839\u79bb\u5b50\uff0c\u6781\u5927\u964d\u4f4e\u4e86CO2<\/sub>\u7684\u5229\u7528\u7387<\/strong>\u3002\u4e3a\u4e86\u63d0\u9ad8CO2<\/sub>\u7684\u5229\u7528\u6548\u7387\uff0c\u8fd1\u5e74\u6765\u5c1d\u8bd5\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u8fdb\u884cCO2<\/sub>R\u53d7\u5230\u8d8a\u6765\u8d8a\u591a\u7684\u5173\u6ce8\u3002<\/p>\n

\u5c3d\u7ba1\u9178\u6027\u73af\u5883\u53ef\u4ee5\u6709\u6548\u9632\u6b62\u78b3\u9178\u6839\u6216\u78b3\u9178\u6c22\u6839\u7684\u5f62\u6210\uff0c\u63d0\u9ad8CO2<\/sub>\u5229\u7528\u7387\uff0c\u4f46\u662f\u9ad8[H+<\/sup>]\u4f7f\u5f97\u6291\u5236\u7ade\u4e89\u53cd\u5e94HER\u5c24\u4e3a\u56f0\u96be\u3002\u5927\u90e8\u5206\u7684\u7814\u7a76\u5de5\u4f5c\u91c7\u7528\u5728\u9178\u6027\u6eb6\u6db2\u4e2d\u6dfb\u52a0\u6781\u5927\u78b1\u91d1\u5c5e\u7535\u89e3\u8d28\u6d53\u5ea6\uff08[M+<\/sup>]>1M\uff09\u7684\u7b56\u7565\u6765\u6291\u5236HER\u63d0\u9ad8CO2<\/sub>R\u7684\u9009\u62e9\u6027\u3002\u5176\u6240\u8c13\u7684\u201c\u9633\u79bb\u5b50\u6548\u5e94\u201c\u4e3b\u8981\u7531\u4ee5\u4e0b\u63d0\u51fa\u7684\u4e09\u79cd\u7406\u8bba\u5047\u8bbe\u6765\u89e3\u91ca\uff1a<\/p>\n

\uff08i\uff09M+<\/sup>\u53ef\u4ee5\u901a\u8fc7\u77ed\u7a0b\u9759\u7535\u76f8\u4e92\u4f5c\u7528\u6216\u76f4\u63a5\u6210\u952e\u6765\u7a33\u5b9a\u50ac\u5316\u5242\u8868\u9762\u5438\u9644\u7684CO2<\/sub>\u5206\u5b50\u6216\u662f\u53cd\u5e94\u4e2d\u95f4\u7269\uff1b<\/p>\n

\uff08ii\uff09M+<\/sup>\u805a\u96c6\u5728outer-Helmholt\u5c42\uff0c\u589e\u5f3a\u4e86\u5c40\u90e8\u7535\u573a\u5f3a\u5ea6\uff0c\u4ece\u800c\u6709\u6548\u7a33\u5b9a\u50ac\u5316\u5242\u8868\u9762\u5438\u9644\u7684\u6781\u6027CO2<\/sub>R\u4e2d\u95f4\u4f53\uff1b\u540c\u65f6\u8fd9\u4e9b\u805a\u96c6\u7684M+<\/sup>\u53ef\u4ee5\u6709\u6548\u5c4f\u853d\u7535\u6781\u4ea7\u751f\u7684\u7535\u573a\uff0c\u6291\u5236H+<\/sup>\u5411\u7535\u6781\u8868\u9762\u7684\u8fc1\u79fb\uff1b<\/p>\n

\uff08iii\uff09\u4e0d\u540cM+<\/sup>\u6240\u914d\u4f4d\u7684\u6c34\u5206\u5b50\u5177\u6709\u4e0d\u540c\u7684pKa<\/sub>\uff0c\u53ef\u4ee5\u6c34\u89e3\u7f13\u51b2\u8c03\u8282\u5c40\u90e8pH\u503c\uff0c\u51cf\u5c11\u78b3\u9178\u6839\u7684\u5f62\u6210\u5e76\u4fdd\u6301\u5408\u9002\u7684\u5c40\u90e8[CO2<\/sub>]\u3002<\/p>\n

\u4f46\u662f\u8f83\u9ad8\u7684[M+<\/sup>]\u4f1a\u5728CO2<\/sub>R\u8fc7\u7a0b\u4e2d\u4ea7\u751f\u78b3\u9178\u76d0\u6c89\u6dc0\u5f71\u54cd\u50ac\u5316\u4f53\u7cfb\u6d3b\u6027\u548c\u7a33\u5b9a\u6027\uff0c\u540c\u65f6\u9ad8\u6d53\u5ea6\u9ad8\u7eaf\u5ea6\u7684M+<\/sup>\u7535\u89e3\u8d28\u6eb6\u6db2\u4e5f\u6781\u5927\u589e\u52a0\u7684\u5e94\u7528\u6210\u672c\u3002\u8042\u4f1f\u8f69\u535a\u58eb<\/strong>\u7684\u524d\u671f\u5de5\u4f5c\uff08Angew. Chem. Int. Ed., 2023,\u200262, e202216102<\/em><\/strong>\uff09\u66fe\u91c7\u7528\u6709\u673a\u819c\u4fee\u9970\u7535\u6781\u7684\u65b9\u6cd5\uff0c\u5b9e\u73b0\u5728\u5f3a\u9178\u6eb6\u6db2\u4f4e[M+<\/sup>]\u4e2d\u9ad8\u6548\u7684CO2<\/sub>\u50ac\u5316\u8fd8\u539f<\/strong>\u3002\u5728\u6b64\u57fa\u7840\u4e0a\uff0c\u8be5\u5de5\u4f5c\u5229\u7528\u7535\u5316\u5b66\u6d4b\u8bd5\u65b9\u6cd5\u7ed3\u5408in-situ \u5149\u8c31\u624b\u6bb5<\/strong>\uff1a\u8868\u9762\u589e\u5f3a\u7ea2\u5916\u5149\u8c31<\/strong>\uff08attenuated total reflection surface-enhanced infrared absorption spectroscopy\uff0cATR-SEIRAS<\/strong>\uff09\u4ee5\u53ca\u8367\u5149\u5171\u805a\u7126\u6fc0\u5149\u626b\u63cf\u663e\u5fae\u955c<\/strong>\uff08fluorescent confocal laser scanning microscopy\uff0cCLSM<\/strong>\uff09\u8fdb\u4e00\u6b65\u63a2\u7a76\u9178\u6027\u6761\u4ef6\u4e0bCO2<\/sub>R\u7684\u5fc5\u8981\u6761\u4ef6<\/strong>\u4ee5\u53caM+<\/sup>\u7684\u4f5c\u7528\u3002<\/p>\n

\u3010\u7814\u7a76\u4eae\u70b9\u3011<\/u><\/strong><\/p>\n

\u8be5\u5de5\u4f5c\u7814\u7a76\u53d1\u73b0\uff0c\u5728\u6ca1\u6709M+<\/sup>\u7684\u9178\u6027\u6eb6\u6db2\u4e2d\uff0c\u5927\u7535\u6d41\u7535\u89e3\u6761\u4ef6\u4e0b\u4ecd\u7136\u53ef\u4ee5\u5b9e\u73b0CO2<\/sub>R<\/strong>\u3002\u8fd9\u662f\u56e0\u4e3a\u8f83\u5927\u7684\u7535\u6d41\u53ef\u4ee5\u5feb\u901f\u6d88\u8017\u7535\u6781\u8868\u9762\u7684[H+<\/sup>] (Figure 1a<\/strong>)\uff0c\u7531\u4e8e\u6765\u4e0d\u53ca\u5f97\u5230H+<\/sup>\u7684\u6269\u6563\u8865\u5145\uff0c\u5f62\u6210\u5c40\u90e8\u975e\u9178\u6027\u7684\u73af\u5883<\/strong>\uff0c\u52a8\u529b\u5b66\u76f8\u5bf9\u7f13\u6162\u7684H2<\/sub>O Reduction \u53cd\u5e94\u4ee3\u66ff\u7684HER\uff0c\u4f7f\u5f97CO2<\/sub>R\u6709\u673a\u4f1a\u53d1\u751f\u3002\u56e0\u6b64\uff0c\u8be5\u5de5\u4f5c\u53d1\u73b0\uff1a\u5feb\u901f\u6d88\u8017\u8868\u9762[H+<\/sup>]\u5e76\u6709\u6548\u7ef4\u6301\u5c40\u90e8\u975e\u9178\u6027\u73af\u5883\uff0c\u662f\u5b9e\u73b0\u9178\u6027\u7535\u89e3\u6db2\u4e2dCO2<\/sub>R\u7684\u524d\u63d0\u6761\u4ef6<\/strong>\u3002\u539f\u4f4d\u7684ATR-SEIRAS <\/strong>\u548c CLSM <\/strong>\u6d4b\u8bd5\u90fd\u8bc1\u5b9e\u4e86\u5927\u7535\u6d41\u4e0b\u7535\u6781\u8868\u9762\u5c40\u90e8pH \u4e0a\u5347\uff0c\u4ece\u800c\u624d\u80fd\u89c2\u6d4b\u5f97\u5230CO\u7684\u4ea7\u751f\u3002<\/p>\n

\"\"<\/p>\n

Figure 1<\/strong>. Strategies to access and promote CO2R in acidic electrolytes are probed in the study. We find that for CO2R to occur on Cu under bulk acidic conditions, the local [H+] must be depleted. Such a microenvironment may be induced by (a) high current; (b) added [M+] to generate a local electric field; and (c) organic film-coated electrodes. Gray, red, white, and blue spheres represent C, O, H, and K atoms, respectively. Black arrows represent the relative H+ transport to the cathode surface for each scenario<\/p>\n

\u52a0\u5165K+<\/sup>\u53ef\u4ee5\u63d0\u9ad8\u7535\u6781\u8868\u9762\u7684pH\u503c<\/strong>\uff08ATR-SEIRAS <\/strong>\u548c CLSM <\/strong>\u6d4b\u8bd5\u8bc1\u5b9e\uff09\uff0c\u4ece\u800c\u89c2\u6d4b\u5230CO2<\/sub>R\uff0cCO2<\/sub>R\u7684\u6cd5\u62c9\u5229\u6548\u7387FE\u4e0eK+<\/sup>-Free\u7684\u6eb6\u6db2\u76f8\u6bd4\u6709\u6240\u63d0\u9ad8\uff0c\u7136\u800cHER\u4ecd\u7136\u5360\u636e\u4e3b\u5bfc\u3002ATR-SEIRAS <\/strong>\u7ed3\u679c\u663e\u793a\u5728\u6240\u52a0\u5165\u7684[K+<\/sup>]\u8303\u56f4\u5185\uff0c\u7535\u6781\u8868\u9762\u7684\u7535\u573a\u5f3a\u5ea6\u4fdd\u6301\u4e0d\u53d8\uff0c\u56e0\u6b64\u8fdb\u4e00\u6b65\u8bc1\u5b9e\uff0cK+<\/sup>\u5bf9CO2<\/sub>R FE\u7684\u63d0\u5347\u5e76\u4e0d\u662f\u6765\u6e90\u4e8eM+<\/sup>\u7684\u5c40\u90e8\u7535\u573a\u589e\u5f3a\u6548\u5e94\uff0c\u800c\u662f\u6709\u6548\u6291\u5236H+<\/sup>\u5411\u7535\u6781\u8868\u9762\u7684\u6269\u6563\u8f6c\u79fb\uff0c\u5f62\u6210\u5c40\u90e8\u975e\u9178\u6027\u73af\u5883 (Figure 1b)<\/strong>\u3002\u7136\u800cK+<\/sup>\u7684\u52a0\u5165\u4f1a\u4f7f\u5f97\u5c40\u90e8pH\u6301\u7eed\u4e0a\u5347\uff0c\u4ece\u800c\u964d\u4f4e[CO2<\/sub>]\uff0c\u56e0\u6b64\u9700\u8981\u5f00\u53d1\u51fa\u5176\u4ed6\u6709\u6548\u8c03\u63a7\u5c40\u90e8pH\u7684\u7b56\u7565\u3002<\/p>\n

\u57fa\u4e8e\u4ee5\u4e0a\u7684\u53d1\u73b0\u548c\u8ba4\u8bc6\uff0c\u8be5\u5de5\u4f5c\u91c7\u7528\u6709\u673a\u819c\u6750\u6599\u4fee\u9970\u7535\u6781\u8868\u9762\u7684\u5fae\u73af\u5883\uff0c\u9009\u62e9\u7684\u6709\u673a\u819c\u53ef\u4ee5\u5f88\u6709\u6548\u7684\u6291\u5236H+<\/sup>\u7684\u8de8\u819c\u6269\u6563\u8f6c\u79fb\uff0c\u5728\u4e0d\u501f\u52a9M+<\/sup>\u548c\u5927\u7535\u6d41\u7684\u60c5\u51b5\u4e0b\u6709\u6548\u5b9e\u73b0\u5c40\u90e8\u975e\u9178\u6027\u73af\u5883 (Figure 1c)<\/strong>\u3002\u5728\u6709\u819c\u7684\u5b58\u5728\u4e0b\uff0c\u53ea\u9700\u52a0\u5165\u5c11\u91cf\u7684K+<\/sup>\uff0820 mM\uff09\u4fbf\u53ef\u4ee5\u6781\u5927\u63d0\u5347\u5f3a\u9178\u6027\u6eb6\u6db2\u4e2d\uff08pH~1\uff09CO2<\/sub>R FE \uff08~65%\uff09\uff0c\u4e3a\u5b9e\u73b0\u9178\u6027\u73af\u5883\u4f4e\u6d53\u5ea6[M+<\/sup>]\u6761\u4ef6\u4e0b\u9ad8\u9009\u62e9\u6027\u7684CO2<\/sub>R \u63d0\u4f9b\u4e86\u5d2d\u65b0\u7684\u601d\u8def\u3002<\/p>\n

\u3010\u7ed3\u679c\u4e0e\u8ba8\u8bba\u3011<\/u><\/strong><\/p>\n

\u5229\u7528ATR-SEIRAS \u548c CLSM \u89c2\u6d4b\u4e0d\u540c\u7a7a\u95f4\u5c3a\u5ea6\uff08\u7a7a\u95f4\u5206\u8fa8\u7387\uff09\u4e0b\u7684pH\u53d8\u5316<\/strong><\/p>\n

\u8be5\u5de5\u4f5c\u6240\u91c7\u7528\u7684ATR-SEIRAS <\/strong>\u548c CLSM <\/strong>\u7684\u6d4b\u8bd5\u624b\u6bb5\u53ef\u4ee5\u5728\u4e0d\u540c\u7684\u7535\u6781\u7535\u4f4d\u4e0b\u4ee5\u53ca\u4e0d\u540c\u7684\u53cd\u5e94\u65f6\u95f4\u70b9\u8fdb\u884c\u539f\u4f4d\u6d4b\u91cfpH\u7684\u6539\u53d8\u3002\u4e0d\u540c\u7684\u662f\uff0cCLSM<\/strong>\u7684\u7a7a\u95f4\u5206\u8fa8\u7387\u8f83\u9ad8\uff08~500 nm\uff09\uff0c\u53ef\u4ee5\u7528\u6765\u89c2\u6d4b\u6269\u6563\u5c42\uff08diffusion layer\uff09\u4e2dpH\u7684\u53d8\u5316\u60c5\u51b5; \u800cATR-SEIRAS<\/strong> \u4e00\u822c\u5173\u6ce8\u4e8e\u7535\u6781\u8868\u9762\u50ac\u5316\u53cd\u5e94\u7684\u7a7a\u95f4\u5c3a\u5ea6\uff081~10nm\uff09\uff0c\u56e0\u6b64\u53ef\u4ee5\u7528\u6765\u89c2\u6d4b\u7535\u6781\u8868\u9762\u53cc\u7535\u5c42\u5fae\u73af\u5883\u4e2d\u7684pH\u6539\u53d8\u3002\u8be5\u5de5\u4f5c\u7684\u6d4b\u8bd5\u90fd\u5728H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\u8fdb\u884c\uff0c\u4e0d\u540c\u7684pH\u5229\u7528KOH\u8c03\u8282\u3002ATR-SEIRAS<\/strong> \u5229\u7528\u4e0d\u540cpH\u73af\u5883\u4e2dH2<\/sub>PO4<\/sub>–<\/sup>\uff0cHPO4<\/sub>2-<\/sup>\u4ee5\u53caPO4<\/sub>3-<\/sup>\u4e2dv<\/em>a<\/sub>(P-O)\u4e0d\u540c\u7684\u7279\u5f81\u5cf0\u4f4d\u7f6e\u548c\u5f3a\u5ea6\u6bd4\u4f8b\uff0c\u6765\u6807\u5b9a\u8be5\u5de5\u4f5c\u4e2d\u7535\u6781\u8868\u9762\u7684pH\u73af\u5883\uff08Figure 2a-2b<\/strong>\uff09\u3002\u800cCLSM<\/strong>\u5219\u5229\u7528\u5177\u6709\u8367\u5149\u8272\u7d20DHPDS\u5728\u4e0d\u540cpH\u4e0b\u8367\u5149\u6ce2\u957f\u7684\u6539\u53d8\u6765\u6807\u5b9a\u7535\u6781\u6269\u6563\u5c42\u4e2d\u6eb6\u6db2\u7684\u5e73\u5747pH\u73af\u5883\uff08Figure 2c-2d<\/strong>\uff09\u3002<\/p>\n

\"\"<\/p>\n

Figure 2<\/strong>. (a) pH-dependent SEIRA spectra of 0.5 M phosphate solutions with corresponding band assignments; (b) phosphate ion speciation used for pH calculations derived from SEIRA spectra absorption intensity; (c) absorption spectrum as a function of pH showing the two excitation wavelengths for fluorescent dye 6,8- dihydroxypyrene-1,3-disulfonic acid disodium salt (DHPDS); and (d) calibration curve for the local pH based on the ratio of emission of the dye and chemical structure of DHPDS<\/p>\n

\u5728\u6ca1\u6709M+<\/sup>\u7684\u9178\u6027\u7535\u89e3\u6db2\u4e2d\u7684CO2<\/sub>R<\/strong><\/p>\n

\u5728CO2<\/sub>\u6c1b\u56f4\u4e0b\u7684pH=2 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\uff0c\u8be5\u5de5\u4f5c\u91c7\u7528Cu\u7535\u6781\uff0c\u5728\u4e0d\u540c\u7535\u6d41\u5f3a\u5ea6\u4e0b\u8fdb\u884c\u63a7\u5236\u7535\u6d41\u7684\u7535\u89e3\u5b9e\u9a8c\uff08controlled-current electrolysis\uff09\u3002\u5b9e\u9a8c\u7ed3\u679c\u663e\u793a\uff0c\u5728\u4f4e\u7535\u6d41\u5f3a\u5ea6\uff08-1.25 mA\/cm2<\/sup>\uff09\u548c\u4e2d\u7b49\u7535\u6d41\u5f3a\u5ea6\uff08-5mA\/cm2<\/sup>\uff09\u4e0b\u90fd\u4e0d\u80fd\u4ea7\u751fCO2<\/sub>R\u7684\u6c14\u76f8\u6216\u662f\u6db2\u76f8\u4ea7\u7269\u3002\u4f46\u662f\u5728\u9ad8\u7535\u6d41\u5f3a\u5ea6\u4e0b\uff08-10mA\/cm2<\/sup>\uff09\uff0c\u5b9e\u9a8c\u89c2\u6d4b\u5230\u4e86\u6c14\u76f8\u4ea7\u7269\uff08CO\uff0cCH4<\/sub>\uff09\u4ee5\u53ca\u6db2\u76f8\u4ea7\u7269\uff08\u7532\u9178\uff09\uff0c\u5c3d\u7ba1FE\u6bd4\u8f83\u4f4e\uff080.4%\uff09\u3002\u8fd9\u4e00\u70b9\u4e5f\u88abin-situ\u8fdb\u884c\u7684SEIRA<\/strong>\u6d4b\u8bd5\u7ed3\u679c\u6240\u8bc1\u5b9e\uff1a\u53ea\u6709\u5728\u5927\u7535\u6d41\u5f3a\u5ea6\u4e0b\uff08-10mA\/cm2<\/sup>\uff09\u663e\u793a\u51fa*CO\u7684\u632f\u52a8\u5438\u6536\u5cf0\uff08Figure 3a<\/strong>\uff09\u3002\u5728\u6d4b\u8bd5\u4e2d\uff0c\u7535\u6781\u7535\u538bE vs.\u65f6\u95f4time\u7684\u66f2\u7ebf\u4e2d\u663e\u793a\uff0c\u5728\u5927\u7535\u6d41\u4e0b\uff0c\u5f53\u7535\u6781\u7535\u538b\u8fbe\u5230\u5e76\u8d85\u8fc7-1.4VRHE<\/sub>\u65f6\uff0c\u624d\u5f00\u59cb\u89c2\u6d4b\u5230CO2<\/sub>R\u7684\u4ea7\u7269<\/strong>\u3002\u4f9d\u636e\u4e4b\u524d\u7684\u6587\u732e\u62a5\u9053\uff0c\u5f53\u7535\u6781\u7535\u4f4d\u8fbe\u5230-1.4VRHE<\/sub>\u65f6\uff0cH2<\/sub>O\u8fd8\u539f\u8fc7\u7a0b\uff08H2<\/sub>ORR\uff09\u66ff\u4ee3H+<\/sup>\u8fd8\u539f\uff08HER\uff09\uff0c\u8868\u660e\u5c40\u90e8\u7684[H+<\/sup>]\u88ab\u6d88\u8017\uff0c\u5c40\u90e8pH\u73af\u5883\u53d8\u6210\u975e\u9178\u6027\u73af\u5883\u3002\u8fd9\u4e00\u70b9\u7531in-situ ATR-SEIRAS<\/strong> \u7ed3\u679c\u8bc1\u5b9e\uff08Figure 3b<\/strong>\uff09\uff1a\u5728\u4f4e\/\u4e2d\u7b49\u7535\u6d41\u5f3a\u5ea6\u4e0b\uff08-1.25\uff0c-5.0 mA\/cm2<\/sup>\uff09\uff0c\u7535\u6781\u8868\u9762\u7684pH\u672a\u6709\u660e\u663e\u6539\u53d8\uff08pH\u663e\u793a\u4e3a4\u662f\u56e0\u4e3aATR-SEIRAS<\/strong>\u7684\u6d4b\u8bd5\u8303\u56f4pH=4~13, pH<4 \u90fd\u663e\u793a\u4e3a4\uff09\uff1b\u800c\u5728\u5927\u7535\u6d41\u4e0b\uff0cpH\u8fc5\u901f\u4e0a\u5347\u81f36.5\u3002\u5728\u4e0d\u540c\u7535\u6d41\u5f3a\u5ea6\u4e0b\u7684pH\u6539\u53d8\u4e5f\u5728CLSM<\/strong>\u7684\u6d4b\u8bd5\u7ed3\u6784\u4e2d\u88ab\u8bc1\u5b9e\uff08Figure 3c<\/strong>\uff09\u3002\u540c\u65f6\uff0cATR-SEIRAS<\/strong>\u7684\u6d4b\u8bd5\u7ed3\u679c\u53d1\u73b0\uff0c*CO\u4fe1\u53f7\u7684\u51fa\u73b0\u4e5f\u4e0e\u8868\u9762pH\u7684\u5347\u9ad8\u4ee5\u53ca\u7535\u6781\u7535\u538b\u964d\u81f3-1.4VRHE<\/sub> \u76f8\u5173\uff08Figure 3d<\/strong>\uff09\u3002<\/p>\n

\"\"<\/p>\n

Figure 3.<\/strong> (a) SEIRA spectra of the adsorbed CO region after 5 min of applied \u27e8j<\/em>\u27e9 in pH 2 H3PO4; (b) interfacial pH as a function of time and \u27e8j<\/em>\u27e9 in pH 2 H3PO4 extracted from SEIRAS data; (c) local pH as a function of time and \u27e8j<\/em>\u27e9 in pH 2 H3PO4 extracted from CLSM data; and (d) local pH (black points) and *CO band intensity (blue points) as a function of potential in pH 2 H3PO4 extracted from SEIRAS data. Note pH 4 is the lower limit of detection for the phosphate system, and therefore, pH values < 4 will appear as pH 4, although they could be much lower.<\/p>\n

\u4e3a\u4e86\u8fdb\u4e00\u6b65\u8bc1\u5b9eCO2<\/sub>R\u53ef\u4ee5\u5728\u6ca1\u6709M+<\/sup>\u9178\u6027\u7535\u89e3\u6db2\u4e2d\u53d1\u751f\uff0c\u8be5\u5de5\u4f5c\u5229\u7528CO2<\/sub>\u4f20\u8d28\u66f4\u4f73\u7684Cu\u6269\u6563\u7535\u6781\uff08Cu-GDE\uff09\uff0c\u5728pH=2 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\uff0c\u5728-10mA\/cm2<\/sup>\u7535\u6d41\u7535\u89e3\u4e0b\u68c0\u6d4b\u5230CO2<\/sub>R FE = 19.8%\u3002\u4e3a\u4e86\u6392\u9664\u6eb6\u6db2\u4e2d\u96be\u4ee5\u907f\u514d\u7684M+<\/sup>\u6742\u8d28\u6df7\u5165\uff08~1ppm\uff09\u4ee5\u53caCu\u79bb\u5b50\u7684\u6eb6\u89e3\uff0c\u8be5\u5de5\u4f5c\u5728H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u52a0\u516510mM \u768418-crown-6\u6765\u6355\u83b7\u8fd9\u4e9b\u6742\u8d28\u91d1\u5c5e\u79bb\u5b50\uff0c\u7ed3\u679c\u5f97\u5230\u76f8\u4f3c\u7684CO2<\/sub>R FE\u3002\u8fd9\u4e00\u7ed3\u679c\u8bf4\u660e\uff0c\u5728pH=2 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u89c2\u6d4b\u5230\u7684CO2<\/sub>R\u5e76\u4e0d\u662f\u7531\u4e8e\u6eb6\u6db2\u4e2d\u7684M+<\/sup>\u6742\u8d28\u6240\u5f15\u8d77\u7684\uff0c\u8fdb\u4e00\u6b65\u8bc1\u5b9e\u4e86 \u5728\u9178\u6027\u6761\u4ef6\u4e0bCO2<\/sub>R\u53d1\u751f\u7684\u524d\u63d0\u6761\u4ef6\u662f\u521b\u9020\u5e76\u7ef4\u6301\u4e00\u4e2a\u975e\u9178\u6027\u7684\u53cd\u5e94\u73af\u5883\u3002<\/strong><\/p>\n

\u5728\u9178\u6027\u6eb6\u6db2\u4e2d\u9010\u6e10\u52a0\u5165M+<\/sup><\/strong><\/p>\n

\u8be5\u5de5\u4f5c\u5728pH=2 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\u9010\u6e10\u52a0\u5165[KCl]\u6765\u8c03\u8282[K+<\/sup>]\uff0c\u7ed3\u679c\u53d1\u73b0\uff0c\u5728\u5c0f\u7535\u6d41\u5bc6\u5ea6\u65f6\uff08-1.25 mA\/cm2<\/sup>\uff09\uff0c\u65e0\u8bba[K+<\/sup>]\u589e\u52a0\u591a\u5927\uff0c\u90fd\u89c2\u6d4b\u4e0d\u90fdCO2<\/sub>R\u7684\u53d1\u751f\u3002\u56e0\u4e3a\u5c0f\u7535\u6d41\u5bc6\u5ea6\u4e0d\u80fd\u6709\u6548\u6d88\u8017\u7535\u6781\u8868\u9762\u7684[H+<\/sup>]\u8425\u9020\u975e\u9178\u6027\u73af\u5883\u3002\u4f46\u662f\u5f53\u7535\u6d41\u589e\u52a0\u65f6\uff0c\u5bf9\u4e8e\u6240\u6709\u7814\u7a76\u7684[K+<\/sup>]\u90fd\u89c2\u6d4b\u5230\u4e86CO2<\/sub>R\u7684\u4ea7\u7269\uff08Figure 4a-4b<\/strong>\uff09\u3002\u540c\u6837\uff0cin-situ ATR-SEIRAS<\/strong> \u7ed3\u679c\u663e\u793a\uff0c\u5f53K+<\/sup>\u52a0\u5165\u540e\uff0c\u7535\u6781\u8868\u9762\u7684pH\u4e0a\u5347\u663e\u793a\u975e\u9178\u6027\u73af\u5883\uff08Figure 4c-4d<\/strong>\uff09\u5e76\u4e14\u89c2\u6d4b\u5230*CO\u7684\u4fe1\u53f7\uff08Figure 4e-4f<\/strong>\uff09\u3002<\/p>\n

\"\"<\/p>\n

Figure 4<\/strong>. (a) CO2R electrolysis product distribution for different [K+] at \u27e8j<\/em>\u27e9 = -5.0 mA\/cm2 in pH 2 H3PO4; (b) CO2R electrolysis product distribution for different [K+] at \u27e8j<\/em>\u27e9 = -10.0 mA\/cm2; (c) interfacial pH as a function of time for different [K+] at \u27e8j<\/em>\u27e9 = -5.0 mA\/cm2; (d) interfacial pH as a function of time for different [K+] at \u27e8j<\/em>\u27e9 = -10.0 mA\/ cm2; (e) time-dependent *CO band intensity for \u27e8j<\/em>\u27e9 = -5.0 mA\/cm2; and (f) time-dependent *CO band intensity for \u27e8j<\/em>\u27e9 = -10.0 mA\/cm2<\/p>\n

\u901a\u8fc7\u5bf9\u4e0d\u540c[K+<\/sup>]\u4e0b*COatop<\/sub>\u7684\u632f\u52a8Stark effect\u7684\u7814\u7a76\u53d1\u73b0\uff08Figure 5a-5c<\/strong>\uff09\uff0cStark \u659c\u7387\u5728\u4e0d\u540c[K+<\/sup>]\u4e0b\u5e76\u6ca1\u6709\u6539\u53d8\uff0c\u8bf4\u660e\u4e0d\u540c[K+<\/sup>]\u4e0b\u7535\u6781\u8868\u9762\u7684\u5c40\u90e8\u7535\u573a\u5f3a\u5ea6\u5e76\u6ca1\u6709\u6539\u53d8\uff0c\u6240\u4ee5\u8bc1\u5b9e\u52a0\u5165K+<\/sup>\u540eCO2<\/sub>R FE\u7684\u63d0\u5347\u5e76\u4e0d\u662f\u7531\u4e8eK+<\/sup>\u5f15\u5165\u7684\u5c40\u90e8\u7535\u573a\u6548\u5e94\u5f15\u8d77\u7684<\/strong>\u3002\u4f46\u662f\u52a0\u5165K+<\/sup>\u540e\uff0c\u7535\u6781\u8868\u9762\u7684\u6eb6\u5242\u6c34\u73af\u5883\u53d1\u751f\u4e86\u660e\u663e\u7684\u6539\u53d8\uff08Figure 5d<\/strong>\uff09\uff1a\u5177\u6709\u8f83\u5f3aH\u952e\u7684\u8868\u9762\u6c34\u5206\u5b50\uff083250cm-1<\/sup>\uff09\u589e\u591a\u800c\u5b64\u7acb\u7684\u6c34\u5206\u5b50\u4ee5\u53ca\u4e0d\u5bf9\u79f0H\u952e\u6c34\u5206\u5b50\uff083600cm-1<\/sup>\u30013400cm-1<\/sup>\uff09\u51cf\u5c11\u3002<\/p>\n

\"\"<\/p>\n

Figure 5<\/strong>. SEIRA spectra of *COatop region as a function of potential and the calculated Stark tuning slopes for (a) 2 mM K+; (b) 20 mM K+; and (c) 200 mM K+. (d) SEIRA spectra for the OH stretching region of the Cu\/electrolyte interface measured at OCV for pH H3PO4 (gray trace) with a background of pure water, and various [K+] with a background of pH 2 H3PO4.<\/p>\n

\u5229\u7528\u6709\u673a\u819c\u4fee\u9970Cu\u7535\u6781\u6765\u63d0\u5347\u9178\u6027\u4f4e[M+<\/sup>]\u6eb6\u6db2\u4e2dCO2<\/sub>R<\/strong><\/p>\n

\u8be5\u5de5\u4f5c\u5728\u7535\u6781\u8868\u9762\u4fee\u9970\u4e86\u4e00\u5c42\u6709\u673a\u819c\uff0c\u8fd9\u5c42\u6709\u673a\u819c\u5728\u66fe\u7ecf\u7684\u5de5\u4f5c\u4e2d\uff08Angew. Chem. Int. Ed., 2023,\u200262, e202216102<\/em><\/strong>\uff09\u88ab\u8bc1\u5b9e\u53ef\u4ee5\u6709\u6548\u7684\u6291\u5236H+<\/sup>\u7684\u8de8\u819c\u4f20\u8d28\u3002\u5728pH=2 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\uff0c\u5728\u6ca1\u6709M+<\/sup>\u7684\u60c5\u51b5\u4e0b\uff0c\u5373\u4f7f\u5728\u5c0f\u7535\u6d41\u5bc6\u5ea6\u4e0b\uff08-1.25 mA\/cm2<\/sup>\uff09\uff0c\u7535\u89e3\u7ed3\u679c\u4ee5\u53cain-situ SEIRA<\/strong>\u6d4b\u8bd5\u7ed3\u679c\u4e5f\u89c2\u6d4b\u5230\u4e86CO2<\/sub>R\u7684\u4ea7\u7269\uff08Figure 6a-6b<\/strong>\uff09\uff0c\u518d\u6b21\u8bc1\u5b9e\u521b\u9020\u5e76\u7ef4\u6301\u4e00\u4e2a\u975e\u9178\u6027\u7684\u53cd\u5e94\u73af\u5883\u5bf9\u4e8e\u9178\u6027\u6761\u4ef6\u4e0bCO2<\/sub>R\u53d1\u751f\u7684\u91cd\u8981\u6027\u3002<\/strong>in-situSEIRA<\/strong>\u6d4b\u8bd5\u4e5f\u89c2\u6d4b\u5230\u4e86\u5728[K+<\/sup>] = 0\u7684pH=2 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\uff0c\u5728\u5c0f\u7535\u6d41\u5bc6\u5ea6\u4e0b\uff08-1.25 mA\/cm2<\/sup>\uff09\uff0c\u6709\u673a\u819c\u4fee\u9970\u7684Cu\u7535\u6781\u8868\u9762pH\u7684\u660e\u663e\u4e0a\u5347\u4ee5\u53ca*CO\u7684\u589e\u52a0\uff08Figure 6c-6d<\/strong>\uff09\u3002\u540c\u65f6\u53d1\u73b0\uff0c\u7535\u6781\u8868\u9762\u7684\u6c34\u73af\u5883\u4e5f\u53d1\u751f\u4e86\u5f88\u5927\u7684\u6539\u53d8\uff08Figure 6e<\/strong>\uff09\uff0c\u663e\u793a\u51fa\u6709\u673a\u819c\u5bf9\u7535\u6781\u8868\u9762\u5fae\u73af\u5883\u7684\u6709\u5229\u8c03\u8282\u3002\u589e\u52a0[K+<\/sup>]\uff0c\u53ef\u4ee5\u8fdb\u4e00\u6b65\u589e\u52a0CO2<\/sub>R FE\uff0c\u4f46\u662f\u53ea\u9700[K+<\/sup>] = 20 mM\uff0cCO2<\/sub>R FE \u4fbf\u53ef\u63d0\u9ad8\u81f3~65%\uff08Figure 6a<\/strong>\uff09\u3002\u5728\u66f4\u52a0\u9178\u6027\u7684pH=1 \u7684H3<\/sub>PO4<\/sub>\u6eb6\u6db2\u4e2d\uff0c\u5229\u7528\u6709\u673a\u819c\u4fee\u9970\u7684Cu-GDE\u4e5f\u80fd\u6709\u6548\u7684\u8fdb\u884cCO2<\/sub>R\uff0c\u53ea\u9700\u8981[K+<\/sup>]=100mM, \u4fbf\u53ef\u4ee5\u8fbe\u5230FEC2+<\/sub> = ~55%\uff0c\u8fd9\u662f\u4ee5\u5f80\u9700\u8981[M+]>1M\u624d\u80fd\u8fbe\u5230\u7684\u6548\u679c\u3002<\/p>\n

\"\"<\/p>\n

Figure 6<\/strong>. (a) Product selectivity at -1.25 mA\/cm2 on Cu\/film electrodes in pH 2 H3PO4 at different [K+]; (b) time-dependent *CO atop formation on Cu\/film electrodes at -1.25 mA\/cm2 in pH 2 H 3PO4 at 0 mM K+; (c) interfacial pH as a function of time for Cu\/film electrodes at -1.25 mA\/cm2 in pH 2 H3PO4 at 0 mM K+; (d) timedependent *CO band area increase on Cu\/film at -1.25 mA\/cm2 in pH 2 H 3PO4 at 0 mM K+; (e) time-dependent OH stretching region of SEIRA spectra during film deposition on Cu at -1.25 mA\/cm2, demonstrating film-induced interfacial water desorption; and (f) product selectivity at -50 mA\/cm2 on Cu-GDE and Cu-GDE\/film electrodes in pH 1 H3PO4 at 0 and 100 mM K+<\/p>\n

\u3010\u4f5c\u8005\u4ecb\u7ecd\u3011<\/u><\/strong><\/p>\n

\u8042\u4f1f\u8f69<\/strong> \u535a\u58eb\uff1a2012\u5e74\u30012015\u5e74\u4e8e\u5357\u4eac\u5927\u5b66\u83b7\u5f97\u5316\u5b66\u4e13\u4e1a\u7406\u5b66\u5b66\u58eb\u5b66\u4f4d\u3001\u65e0\u673a\u5316\u5b66\u4e13\u4e1a\u7855\u58eb\u5b66\u4f4d\u3002 2015 \u2013 2021\u5e74\u5728\u7f8e\u56fd\u5bc6\u6b47\u6839\u5927\u5b66\uff08University of Michigan, Ann Arbor\uff09\u653b\u8bfb\u65e0\u673a\u5316\u5b66\u4e13\u4e1a\u5e76\u83b7\u5f97\u535a\u58eb\u5b66\u4f4d\u30022021\u5e745\u6708\u8d77\u5728\u7f8e\u56fd\u52a0\u5dde\u7406\u5de5\u5b66\u9662 (California Institute of Technology, Caltech)\uff0c\u52a0\u76df\u7f8e\u56fd\u80fd\u6e90\u90e8\u7ec4\u5efa\u7684\u201c\u6db2\u4f53\u9633\u5149\u7814\u7a76\u8054\u76df\u201d \uff08The Liquid Sunlight Alliance, LiSA\uff09\u4ece\u4e8b\u535a\u58eb\u540e\u7814\u7a76\u5de5\u4f5c\u3002\u66fe\u8363\u83b7\u56fd\u5bb6\u4f18\u79c0\u81ea\u8d39\u7559\u5b66\u751f\u5956\u5b66\u91d1\u3001\u7f8e\u56fd\u5316\u5b66\u4f1a\u65e0\u673a\u5316\u5b66\u9752\u5e74\u5b66\u8005\u5956\uff08ACS Division of Inorganic Chemistry Young Investigator Award\uff09\u3001\u7f8e\u56fd\u5357\u4eac\u5927\u5b66\u6559\u80b2\u57fa\u91d1\u4f1a\u5956\u5b66\u91d1\uff08American NJUEF Scholarship\uff09\u7b49\u5956\u9879\u3002\u8042\u4f1f\u8f69\u535a\u58eb\u4e8e2023\u5e74\u51ac\u5b63\u52a0\u5165\u897f\u6e56\u5927\u5b66\u5de5\u5b66\u9662\u4efb\u7279\u8058\u7814\u7a76\u5458\uff0c\u52a9\u7406\u6559\u6388\uff0c\u72ec\u7acbPI\uff0c\u5efa\u7acb\u201c\u7535\u5316\u5b66\u50ac\u5316CO2<\/sub>\u8f6c\u5316\u201d\u5b9e\u9a8c\u5ba4<\/strong>\u3002<\/p>\n

\u8bda\u8058\u5404\u9636\u6bb5\u7684\u5b66\u8005\uff0c\u5305\u62ec\u535a\u58eb\u540e\u3001\u535a\u58eb\u7814\u7a76\u751f\u3001\u7814\u7a76\u52a9\u7406\u3002\u6b22\u8fce\u5bf9\u8be5\u7814\u7a76\u65b9\u5411\u611f\u5174\u8da3\uff0c\u5177\u6709\u5316\u5b66\u5408\u6210\u3001\u7535\u5316\u5b66\u50ac\u5316\uff0c\u5206\u5b50\u8bbe\u8ba1\uff0c\u6750\u6599\u79d1\u5b66\u6216\u5316\u5b66\u5de5\u7a0b\u80cc\u666f\u7684\u5b66\u8005\u52a0\u5165\uff0c\u8bf7\u901a\u8fc7\u7535\u5b50\u90ae\u4ef6\u8054\u7cfb\u5e76\u9644\u4e0a\u7b80\u5386\u3002\u7535\u5b50\u90ae\u7bb1\uff1anieweixuan@westlake.edu.cn<\/a>\uff1b\u8bfe\u9898\u7ec4\u7f51\u9875\uff1ahttps:\/\/www.westlake.edu.cn\/faculty\/weixuan-nie.html<\/a><\/p>\n","protected":false},"excerpt":{"rendered":"

\u7b2c\u4e00\u4f5c\u8005\uff1aMadeline H. Hicks \u548c Dr. Weixuan Nie (\u8042\u4f1f\u8f69 \u535a\u58eb\uff0c\u73b0\u4e3a\u897f\u6e56\u5927\u5b66\u5de5\u5b66\u9662PI\/\u535a\u58eb\u751f\u5bfc\u5e08\uff0c\u6587\u672b\u9644\u6709\u4f5c\u8005\u4ecb\u7ecd) \u901a\u8baf\u4f5c…<\/p>\n","protected":false},"author":2,"featured_media":0,"comment_status":"open","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[215],"tags":[],"class_list":["post-262355","post","type-post","status-publish","format-standard","hentry","category-jiedu"],"_links":{"self":[{"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts\/262355"}],"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\/2"}],"replies":[{"embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=262355"}],"version-history":[{"count":2,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts\/262355\/revisions"}],"predecessor-version":[{"id":262365,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=\/wp\/v2\/posts\/262355\/revisions\/262365"}],"wp:attachment":[{"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=262355"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=262355"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/www.cailiaoniu.com\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=262355"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}