当前位置:首页>南京>南京大学金钟教授团队AFM:原位重构的铋纳米花显著增强电催化二氧化碳还原性能

南京大学金钟教授团队AFM:原位重构的铋纳米花显著增强电催化二氧化碳还原性能

  • 2026-04-11 05:37:54
南京大学金钟教授团队AFM:原位重构的铋纳米花显著增强电催化二氧化碳还原性能

导语

金属铋(Bi)电催化剂已被证明可以提高HCOOH的选择性并抑制二氧化碳还原(CO2RR)中的析氢副反应。这些Bi基催化剂通常由前驱体进行转化所得,通过有针对性的界面调控,Bi基催化剂可以形成特殊的纳米结构。然而,Bi基化合物在电催化CO2RR过程中的结构转变机制仍有尚未解明之处。另外,催化的活性中心究竟是Bi0还是Bi3+仍然存在一些争议。此外,在Bi基催化剂相关的研究中,尚未提供对于CO2RR过程中的反应中间体可靠的原位拉曼证据。近日,南京大学化学化工学院金钟教授团队探究了Bi基材料于电催化CO2还原过程中的原位重构过程对活性位点的影响。相关研究成果发布在Advanced Functional Materials上(DOI: 10.1002/adfm.202301984)。

前沿科研成果

原位重构的铋纳米花显著增强电催化二氧化碳还原性能

(图片来源:Advanced Functional Materials
该工作中,首先通过置换反应可以在Cu箔上原位生长Bi@Bi2O3纳米枝晶结构(Bi@Bi2O3-NDs),而这种纳米枝晶在KHCO3溶液中经过电还原后会转变成由弯曲纳米片堆积而成的花状结构(Bi-NFs)。
(图片来源:Advanced Functional Materials
(图片来源:Advanced Functional Materials
为探究这种原位重构过程的机理,作者在不同溶液中对Bi@Bi2O3-NDs进行电还原,发现仅在KHCO3溶液中发生了重构,在KCl与KOH溶液中则无明显变化。此外,仅在KHCO3溶液中还原后,Bi2O3的拉曼信号明显减弱。这些结果证明HCO3-在原位重构过程中起关键作用。
另外,将Bi@Bi2O3-NDs浸泡在KHCO3溶液中,发现其表面产生了许多新的小纳米片。经由EDX、XPS、XRD表征,最终确定这些纳米片的组成为Bi2O2CO3。故而原位重构的过程表现为:首先,Bi@Bi2O3-NDs上的Bi2O3层与HCO3-反应形成Bi2O2CO3纳米片。然后Bi2O2CO3纳米片在负电位下被还原以形成活性Bi0。根据XPS谱图,活性 Bi0并不稳定,在空气中会迅速被再氧化。经过上述反应的几个循环后,枝晶结构会完全重构,使得Bi@Bi2O3-NDs被完全转化为Bi-NFs。
(图片来源:Advanced Functional Materials
通过对比裸铜箔、Bi@Bi2O3-NDs和Bi-NFs的各方面电化学性能,可判定Bi-NFs在经过原位重构后得到了更低的阻抗、更大的电化学活性面积以及更多的活性位点,进而使得电催化CO2转化为甲酸的选择性获得大幅提高。
(图片来源:Advanced Functional Materials
最后,将生长了Bi@Bi2O3-NDs的电极片用于长时间的CO2电还原稳定性测试。在首圈中,Bi@Bi2O3-NDs尚未完成原位重构过程,缺乏对应的活性位点和电化学性能,故而甲酸的法拉第效率偏低。而重构成为Bi-NFs后,甲酸的法拉第效率大幅提高,并且能维持16小时的稳定。这种Bi-NFs的形貌在长循环后也仍能得到保持。
此外,通过原位拉曼光谱,可判明在CO2还原过程中,*OCHO中间体的稳定起到了关键性作用。结合XPS证据,可判断出原位重构的Bi-NFs具有丰富的Bi0活性位点,起到了对*OCHO中间体的稳定吸附作用,进而保证了甲酸的转化路径,最终提高了电催化的选择性。
该工作近期发表在Advanced Functional Materials(DOI: 10.1002/adfm.202301984)。南京大学博士研究生杨淞元江明航为该论文的共同第一作者。上述研究工作得到了国家重点研发计划、国家自然科学基金、江苏省碳达峰碳中和科技创新专项、J科委XXX工程、J科委GF科技创新特区项目的资助。

课题组简介

课题组主要研究方向包括光电催化、液流电池、碱金属电池、多价离子电池等。
课题组官方主页:https://hysz.nju.edu.cn/zhongjin/

教授简介

金钟,南京大学化学化工学院教授、博导,南京大学新材料与能源技术研发中心主任。2003年和2008年分别获得获北京大学学士和博士学位。2008-2014年先后在美国Rice大学和MIT进行博士后研究。2014年起任教于南京大学,入选国家“WR计划”领军人才、优青、青千。主要研究方向是清洁能源转换与存储材料的结构设计、机理研究和器件应用。
Nature Chem.Nature Comm.、JACSAngewChem.、AdvMater.等期刊发表SCI论文>210篇,他引>16000次,H因子64,2021-2022连续两年入选Clarivate全球高被引科学家及Elsevier中国高被引学者。获得了国家自然科学奖二等奖(2021,5/5)、教育部自然科学奖一等奖(2018,4/7)、江苏省科学技术奖三等奖(2021,1/7)、江苏省教育教学与研究成果奖二等奖(2018,1/5)、江苏省首届创新争先奖状、江苏省双创人才、入选全国“大众创业万众创新活动周”核心展区等荣誉。主持国家重点研发计划青年科学家专题、J科委XXX工程、J科委GF科技创新特区项目、装备预研教育部联合基金青年人才项目、国家自然科学基金、江苏省碳达峰碳中和科技创新专项、江苏省杰出青年基金等项目。
担任江苏省化学化工学会理事兼青年工作委员会主任、江苏省能源研究会储能专委会委员、江苏省汽车工程学会动力电池专委会委员、Frontiers in Chemistry副主编、Nanomaterials编委、Nano ResearchSmartMatChinese Chemical LettersJournal of Electrochemistry青年编委等学术任职。 

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  1. CONNECT:[ UseTime:0.000548s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000597s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000318s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000335s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000548s ]
  6. SELECT * FROM `set` [ RunTime:0.000233s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000561s ]
  8. SELECT * FROM `article` WHERE `id` = 528309 LIMIT 1 [ RunTime:0.000463s ]
  9. UPDATE `article` SET `lasttime` = 1777054920 WHERE `id` = 528309 [ RunTime:0.002187s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000276s ]
  11. SELECT * FROM `article` WHERE `id` < 528309 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.000462s ]
  12. SELECT * FROM `article` WHERE `id` > 528309 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.001305s ]
  13. SELECT * FROM `article` WHERE `id` < 528309 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.000701s ]
  14. SELECT * FROM `article` WHERE `id` < 528309 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.000720s ]
  15. SELECT * FROM `article` WHERE `id` < 528309 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.001284s ]
0.084405s