边锋游戏

利用第一性原理设计更好的燃料电池催化剂
发布时间:2019-05-30 12:35:00

利用第一性原理设计更好的燃料电池催化剂


设计高活性定性的电催化剂,一直是燃料电池的主要目标之一。在电催化剂的设计中,必须要注意一些特殊情况,比如氧还原反应缓慢的动力学、纳米颗粒固有的结构不稳定性、以及在严酷电化学条件下的电位等。现如今,形形色色的电催化剂层出不穷,如何快速筛选并优化出最佳至关重要。有鉴于此,韩国延世大学Byungchan Han等在《Current Opinion in Electrochemistry》期刊上发表综述文章,介绍了近年来第一原理计算方法在质子交换膜燃料电池电催化剂设计中的一些进展,包括电催化活性和电化学稳定性,为寻找更优异的质子交换膜燃料电池催化剂打下坚实的基础。作者认为,只有保持创新思维,才能有效突破。

 

【文章背景】


边锋游戏RANLIAODIANCHISHIYIZHONGDIANHUAXUEXITONG,KEYIJIANGCHUCUNZAIRANLIAOZHONGDENENGLIANGZHIJIEZHUANHUAWEIDIANNENG,YULIDIANCHIBUTONGDESHI,RANLIAODIANCHIKEYIZAIRANLIAOGONGYINGDEQINGKUANGXIACHIXUFADIAN,ZHEIDUIQICHEDEZHANGJULIXINGSHIFEICHANGYOUYI。ZHIZIJIAOHUANMO(PEM)RANLIAODIANCHIDEGUANJIANDIANHUAXUEFANYINGRUSHI(1)SUOSHI,QIZHONGQINGQIHEYANGQIFANYING,ZUIZHONGCHANSHENGSHUIHEDIAN:



LILUNSHANG,RANLIAODIANCHINENGLIANGZHUANHUANXIAOLVMEIYOUXIANZHI,DANSHIJISHANG,YOUYUCUNZAIDALIANGDEHUOHUANENGLEI,DIANHUAXUEFANYINGDONGLIXUETEBIEHUANMAN,TEBIESHIORRFANYING。YINCI,BIXUSHIYONGDIANCUIHUAJILAICUJINDIANHUAXUEFANYING。HAOWUYIWEN,ORRGAOXINGNENGDIANCUIHUAJIDEYANFASHIMUQIANCUIHUALINGYUZUIREMENDEFANGXIANGZHIYI,JIBIANSHICHUANTONGSHANGBEICHENGWEIZUIJIACUIHUAJIDEBO,QIORRXIAOLVHECAILIAOCHENGBENYEBUWANQUANFUHEGONGYEBIAOZHUN。YINCI,ZHIZIJIAOHUANMORANLIAODIANCHIDIANCUIHUAJIDEGUANJIANWENTISHIRUHEYIGENGGAODEXIAOLV、GENGDIDEJIAGEHEGENGWENDINGDECUIHUAHUOXINGLAITIDAIPt,JINGUANXUDUOSHIYAN、LILUNMOXINGHEJISUANDEQIANYANLINGYUJINXINGLEXIANGJINDEYANJIU,DANRENGMEIYOUSHANGYEHUACUIHUAJINENGYUBOPIMEI。


边锋游戏ZAIBENWENZHONG,HANGUOYANSHIDAXUEByungchanHanDENGJIANYAOHUIGULEJIYUDIYIYUANLIDEJISUANDUIPEMRANLIAODIANCHIDEYANJIUJINZHAN,ZUOZHERENWEIYAOTAOLUNDEGUANJIANWENTISHI:(i)XUDUODIANCUIHUAJITONGCHANGSHINAMIJIBIEDE,ZAIXIANGHUTUANJUDEQINGKUANGXIA,QIRELIXUEBIANDEHENBUWENDING;(ii)RANLIAODIANCHIDEDIANCUIHUAJITONGCHANGHUIBAOLUYUYIXIEJIDUANTIAOJIANXIA,ZHEIKENENGHUIJIANGDICUIHUAJIDEJIEGOUWENDINGXING;(iii)YINGZHIDINGKUAISU、ZHUNQUEDEXINGSHIHUOFANGFA,YIFENXICONGSHIYANHEJISUANJIEGUOZHONGJILEIDEDASHUJU,KUAISUPINGGUTIDAIDIANCUIHUAJIDECUIHUAHUOXING。

 

【文章详情】


一、预测催化剂的结构和稳定性



第一性原理中的密度泛函理论(DFT)计算,现已广泛应用于预测各种分子、纳米粒子和散装材料在真空条件下的基态结构,如上图1a-c所示,与实验结果的一致性足以证明DFT计算的准确性。然而,考虑到PEM燃料电池中的电催化剂会暴露于非真空溶液中,因此需要采用更恰当的形式来正确地引入变量。


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DUIYURANLIAODIANCHIZHONGDEDIANHUAXUEFANYINGERYAN,BONAMICUIHUAJIDEPourbaixTUKEYITONGGUOYIZHIDENENGSITEFANGCHENGSUANCHU:



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二、评估催化性能


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上图2a,b为立方八面体铂纳米粒子ORR的吉布斯自由能图,结果表明,催化剂的起始电位与表面形貌以及反应中间体密切相关。对于性能而言,只有Pt(111)晶面更好,尤其是单晶。该方法适用于任何纯催化剂或合金催化剂,例如,图2c中显示了六方钙钛矿BaNiO3的ORR催化性能,如图所示,DFT可以通过优化材料结构(形态和组成)以获得所需的最佳催化性能。


在过去的十年中,No边锋游戏rskov提出的电子结构模型,即所谓的“火山图”,已被广泛用于识别最佳ORR催化剂,该理论确定了ORR的关键描述符——氧吸附能(ΔEO)作为控制参数(图2d)。优化ΔEO,对设计高效的铂替代催化剂具有重要意义。值得注意的是,很多文章里描述的催化剂都没有在市场上成功地商业化,主要问题不是催化活性,而是催化剂稳定的结构完整性,这意味着电子结构计算更广泛的应用。

 

三、催化剂设计策略


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LINGYIGEZHIDEZHUYIDECUIHUAJISHIJIEMIANDIAOKONG,JIFEIJINGTAI/JINGTICAILIAO。RUTU4SUOSHI,LIRU,CoP@PS/NCNTHEQIAOCAILIAO,PSDEFEIJINGTAIWAIQIAOYOULIYUKONGZHIQINGYUGUJINSHUZHIJIANDEXIANGHUZUOYONG,CONGERZENGQIANGLEHERDEHUOXING。

 

【文章结论】


边锋游戏ZAIBENWENZHONG,ZUOZHEJIANYAOZONGJIELEJIYUDIYIXINGYUANLIJISUAN,LAIPINGGURANLIAODIANCHIDEDIANCUIHUAXINGNENGDEJINZHAN。ZICONGHUOSHANQUXIANCHUXIANYILAI,RANLIAODIANCHILINGYU10DUONIANQIANRENGRANMEIYOURENHESHANGYEHUACUIHUAJIYITIDAICHUANTONGGUIJINSHUBO。YINCI,WEILEDAPOJIANGJU,SUOJIANYANFACHENGBEN,LIYONGHAOJISUANSHIGUANJIAN。CONGBENZHISHANGSHUO,YINGGAIKAIFAYIGETONGYIDEJISUANPINGTAI,NENGGOUKUAISUFENXISHIYAN,BINGQIEJILEIDAOCAILIAOXINXIXUEDEDASHUJUKUZHONG,YISHIBIEGUANJIANMIAOSHUFUHESHEJIYUANZE。ZHIDEZHUYIDESHI,YOUJIGEKETIZUYIJINGKAISHIXIANGZHEIGEFANGXIANGCHUFA,ZHEISHIFEICHANGYOUQUDE。

 

Seunghyo Noh, Jeemin Hwang, Joonhee Kang and Byungchan Han. First-principles computational approach for innovative design of highly functional electrocatalysts in fuel cells, Current Opinion in Electrochemistry, 2018, 12:225–232, DOI:10.1016/j.coelec.2018.11.016


稿件来源: 能源学人
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