富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐※

doi:10.6023/A22010012

化学学报 ›› 2022, Vol. 80 ›› Issue (6): 703-707.DOI: 10.6023/A22010012 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究通讯

富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐^※

蒋银龙^a^,^b, 李国超^a^,^b, 陈青松^b^,^*(), 徐忠宁^b, 林姗姗^a^,^b, 郭国聪^b^,^*()

a 福州大学化学学院福州 350116
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

投稿日期:2022-01-06 发布日期:2022-07-07
通讯作者: 陈青松, 郭国聪
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家重点研发计划项目(2017YFA0206802); 国家重点研发计划项目(2017YFA0700103); 国家自然科学基金(21203200); 国家自然科学基金(91545201)

Porous Bismuth Nanoflowers Enriched with Lattice Dislocations for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate^※

Yinlong Jiang^a^,^b, Guochao Li^a^,^b, Qingsong Chen^b(), Zhongning Xu^b, Shanshan Lin^a^,^b, Guocong Guo^b()

a College of Chemistry, Fuzhou University, Fuzhou 350116, China
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Received:2022-01-06 Published:2022-07-07
Contact: Qingsong Chen, Guocong Guo
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Key R&D Program of China(2017YFA0206802); National Key R&D Program of China(2017YFA0700103); National Natural Science Foundation of China(21203200); National Natural Science Foundation of China(91545201)

文章分享

1. Supporting Information-A22010012.pdf(2169KB)

摘要/Abstract

二氧化碳转化已成为现今世界研究的热点. 本工作采用原位电化学转化的策略, 将简单溶剂热法合成的层状甲酸氧铋纳米花(BiOCOOH NFs)还原为带有大量晶格位错的多孔铋纳米花(p-Bi NFs). 研究结果表明, p-Bi NFs电催化二氧化碳转化为甲酸盐具有较小的过电位(436 mV). 在–1.8 V(相对饱和甘汞电极, vs. SCE)时, 甲酸盐的分电流密度(j_formate)高达24.4 mA•cm^-2, 法拉第效率(FE_formate)为96.7%, 且在超过500 mV的宽电位窗口内FE_formate超过90%, 并具有很好的稳定性. 该催化剂的高催化性能可归因于前驱体晶格坍塌和重构而形成特殊的多孔粗糙的微纳多级结构, 其表面富含晶格位错和缺陷等高本征活性位, 且具有较强的电子传递能力. 本研究为设计合成高性能的电催化二氧化碳还原产甲酸催化剂提供了新的思路.

关键词: 铋, 电催化, 二氧化碳, 甲酸盐, 晶格位错

The conversion of carbon dioxide has become a hot topic in the world today. Here, we adopt the strategy of in-situ electrochemical transformation to reduce layered bismuth oxide formate nanoflowers (BiOCOOH NFs) self-assembled with nanosheets synthesized by simple solvothermal method to porous bismuth nanoflowers (p-Bi NFs) with a large number of lattice dislocations. Specifically, 1.0 g Bi(NO₃)₃•5H₂O was ultrasonically dissolved in 10 mL N,N-dimethylformamide (DMF), then 70 mL deionized water was added to the above solution, and the resulting solution was ultrasonicated for 10 min at room temperature to ensure that all reagents were uniformly dispersed. The resulting solution was then transferred to a 100 mL Teflon-lined stainless steel autoclave, kept at 120 ℃ for 20 h, and then naturally cooled to room temperature. The results show that the minimum overpotential of the electrochemical reduction of carbon dioxide to formate is 436 mV. When the catalyst loading is 0.5 mg/cm², the partial current density of formate (j_formate) is as high as 24.4 mA•cm^-2, which is 5.5 times that of commercial bismuth (Commercial Bi); and the Faraday efficiency (FE_formate) of formate is 96.7% at –1.8 V versus saturated calomel electrode (vs. SCE). The FE_formate is over 90% in a wide potential window of over 500 mV. Moreover, the p-Bi NFs electrocatalyst is stable in formate production for more than 10 h in CO₂-saturated 0.5 mol•L^-1 KHCO₃ electrolyte. Compared with the normalized electrochemical surface area (ECSA), it was found that the j_formate of p-Bi NFs was still about 4.5 times higher than that of Commercial Bi. The high catalytic performance of the catalyst can be attributed to the unique micro/nano hybrid structure derived from the lattice collapse and reconstruction of precursors, resulting in porous and rough surface and containing high density of active sites with lattice dislocations and defects. This study provides new insights into designing and synthesizing electrocatalysts with high performance for carbon dioxide reduction to formate.

Key words: bismuth, electrocatalysis, carbon dioxide, formate, lattice dislocation

引用此文

蒋银龙, 李国超, 陈青松, 徐忠宁, 林姗姗, 郭国聪. 富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐^※[J]. 化学学报, 2022, 80(6): 703-707.

Yinlong Jiang, Guochao Li, Qingsong Chen, Zhongning Xu, Shanshan Lin, Guocong Guo. Porous Bismuth Nanoflowers Enriched with Lattice Dislocations for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate^※[J]. Acta Chimica Sinica, 2022, 80(6): 703-707.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 3

图1. p-Bi NFs的合成过程示意图

Figure 1. Schematic of the synthesis process of p-Bi NFs

图2. BiOCOOH NFs和p-Bi NFs的结构表征. BiOCOOH NFs和p-Bi NFs的XRD谱图(a); p-Bi NFs的SEM (b)、TEM (c)和HRTEM图像(d), (e)和(f)分别为(d)图中方框区域(1)和(2)的放大图

Figure 2. Structure characterization of BiOCOOH NFs and p-Bi NFs. XRD images of BiOCOOH NFs and p-Bi NFs (a); SEM (b), TEM (c) and HRTEM (d) images of p-Bi NFs. (e) and (f) are respectively the magnification of the white square region (1) and (2) as indicated in (d)

图3. H型电解池中的电化学二氧化碳还原性能测试. p-Bi NFs 和商业化Bi分别在CO2和Ar饱和的0.5 mol•L-1 KHCO3溶液中的线性扫描伏安曲线(LSV) (a); p-Bi NFs和商业化Bi的甲酸盐分电流密度(b)和法拉第效率(c)随电势变化的比较; p-Bi NFs的稳定性测试(d); p-Bi NFs 和商业化Bi的电化学阻抗谱(EIS) (e)及塔菲尔(Tafel)曲线(f)比较

Figure 3. Measurement of electrochemical carbon dioxide reduction performance in H type cell. Linear scanning voltammetric curves (LSV) of p-Bi NFs and Commercial Bi in CO2 and Ar saturated 0.5 mol•L-1 KHCO3 solution (a); comparison of formate current density (b) and Faraday efficiency (c) of p-Bi NFs and Commercial Bi with potential variation; stability test of p-Bi NFs (d); comparison of electrochemical impedance spectroscopy (EIS) (e) and Tafel curve (f) of p-Bi NFs and Commercial Bi

参考文献 31

[1]	Wang, X. S.; Yang, X.; Chen, C. H.; Li, H. F.; Huang, Y. B.; Cao, R. Acta Chim. Sinica 2022, 80, 22. (in Chinese) doi: 10.6023/A21100455
	(王旭生, 杨胥, 陈春辉, 李红芳, 黄远标, 曹荣, 化学学报, 2022, 80, 22.) doi: 10.6023/A21100455
[2]	Chen, Q.; Kuang, Q.; Xie, Z. X. Acta Chim. Sinica 2021, 79, 10. (in Chinese) doi: 10.6023/A20080384
	(陈钱, 匡勤, 谢兆雄, 化学学报, 2021, 79, 10.) doi: 10.6023/A20080384
[3]	Qin, Z. Z.; Wu, J.; Li, B.; Su, T. M.; Ji, H. B. Acta Phys. -Chim. Sin. 2021, 37, 2005027.
[4]	Mu, C. H.; Zhang, Y. X.; Kou, W.; Xu, L. B. Acta Chim. Sinica 2021, 79, 925. (in Chinese) doi: 10.6023/A21030104
	(穆春辉, 张艺馨, 寇伟, 徐联宾, 化学学报, 2021, 79, 925.) doi: 10.6023/A21030104
[5]	Song, B.; Qin, A. J.; Tang, B. Z. Acta Chim. Sinica 2020, 78, 9. (in Chinese) doi: 10.6023/A19090340
	(宋波, 秦安军, 唐本忠, 化学学报, 2020, 78, 9.) doi: 10.6023/A19090340
[6]	Sun, Z.; Ma, T.; Tao, H.; Fan, Q.; Han, B. Chem. Rev. 2017, 3, 560.
[7]	Du, D.; Lan, R.; Humphreys, J.; Tao, S. J. Appl. Electrochem. 2017, 47, 661. doi: 10.1007/s10800-017-1078-x
[8]	Komatsu, S.; Yanagihara, T.; Hiraga, Y.; Tanaka, M.; Kunugi, A. Denki Kagaku 1995, 63, 217.
[9]	Wen, G. B.; Lee, D. U.; Ren, B. H.; Hassan, F. M.; Jiang, G. P.; Cano, Z. P.; Gostick, J.; Croiset, E.; Bai, Z. Y.; Yang, L.; Chen, Z. W. Adv. Energy Mater. 2018, 8, 1802427. doi: 10.1002/aenm.201802427
[10]	Zhou, J. H.; Yuan, K.; Zhou, L.; Guo, Y.; Luo, M. Y.; Guo, X. Y.; Meng, Q. Y.; Zhang, Y. W. Angew. Chem. Int. Ed. 2019, 58, 14197. doi: 10.1002/anie.201908735
[11]	Lamagni, P.; Miola, M.; Catalano, J.; Hvid, M. S.; Mamakhel, M. A. H.; Christensen, M.; Madsen, M. R.; Jeppesen, H. S.; Hu, X. M.; Daasbjerg, K.; Skrydstrup, T.; Lock, N. Adv. Funct. Mater. 2020, 30, 1910408. doi: 10.1002/adfm.201910408
[12]	Zhang, X. L.; Sun, X. H.; Guo, S. X.; Bond, A. M.; Zhang, J. Energy Environ. Sci. 2019, 12, 1334. doi: 10.1039/C9EE00018F
[13]	Gong, Q. F.; Ding, P.; Xu, M. Q.; Zhu, X. R.; Wang, M. Y.; Deng, J.; Ma, Q.; Han, N.; Zhu, Y.; Lu, J.; Feng, Z. X.; Li, Y. F.; Zhou, W.; Li, Y. G. Nat. Commun. 2019, 10, 2807. doi: 10.1038/s41467-019-10819-4
[14]	Fan, K.; Jia, Y. F.; Ji, Y. F.; Kuang, P. Y.; Zhu, B. C.; Liu, X. Y.; Yu, J. G. ACS Catal. 2020, 10, 358. doi: 10.1021/acscatal.9b04516
[15]	Yang, H.; Han, N.; Deng, J.; Wu, J. H.; Wang, Y.; Hu, Y. P.; Ding, P.; Li, Y. F.; Li, Y. G.; Lu, J. Adv. Energy Mater. 2018, 8, 1801536. doi: 10.1002/aenm.201801536
[16]	Zhang, W. J.; Hu, Y.; Ma, L. B.; Zhu, G. Y.; Zhao, P. Y.; Xue, X. L.; Chen, R. P.; Yang, S. Y.; Ma, J.; Liu, J.; Jin, Z. Nano Energy 2018, 53, 808. doi: 10.1016/j.nanoen.2018.09.053
[17]	Peng, C. J.; Zeng, G.; Ma, D. D.; Cao, C. S.; Zhou, S. H.; Wu, X. T.; Zhu, Q. L. ACS Appl. Mater. Interfaces 2021, 13, 20589. doi: 10.1021/acsami.1c03871
[18]	He, Y. C.; Ma, D. D.; Zhou, S. H.; Zhang, M.; Tian, J. J.; Zhu, Q. L. Small 2021, 18, 2105246. doi: 10.1002/smll.202105246
[19]	Han, N.; Wang, Y.; Yang, H.; Deng, J.; Wu, J. H.; Li, Y. F.; Li, Y. G. Nat. Commun. 2018, 9, 1320. doi: 10.1038/s41467-018-03712-z pmid: 29615621
[20]	Liu, J. Z.; Li, Y. H.; Wang, Y. T.; Xiao, C. Q.; Liu, M. M.; Zhou, X. D.; Jiang, H.; Li, C. Z. Nano Res. 2022, 15, 1409. doi: 10.1007/s12274-021-3677-4
[21]	Koh, J. H.; Won, D. H.; Eom, T.; Kim, N. K.; Jung, K. D.; Kim, H.; Hwang, Y. J.; Min, B. K. ACS Catal. 2017, 7, 5071. doi: 10.1021/acscatal.7b00707
[22]	Fan, M. Y.; Prabhudev, S.; Garbarino, S.; Qiao, J. L.; Botton, G. A.; Harrington, D. A.; Tavares, A. C.; Guay, D. Appl. Catal. B 2020, 274, 119031. doi: 10.1016/j.apcatb.2020.119031
[23]	Yang, F.; Elnabawy, A. O.; Schimmenti, R.; Song, P.; Wang, J. W.; Peng, Z. Q.; Yao, S.; Deng, R. P.; Song, S. Y.; Lin, Y.; Mavrikakis, M.; Xu, W. L. Nat. Commun. 2020, 11, 2352. doi: 10.1038/s41467-020-16260-2 pmid: 32376897
[24]	Liu, P.; Liu, H. L.; Zhang, S.; Wang, J.; Wang, C. J. Colloid Interface Sci. 2021, 602, 740. doi: 10.1016/j.jcis.2021.06.010
[25]	Duan, F.; Zheng, Y.; Liu, L. A.; Chen, M. Q.; Xie, Y. Mater. Lett. 2010, 64, 1566. doi: 10.1016/j.matlet.2010.04.046
[26]	Yang, J.; Wang, X. L.; Qu, Y. T.; Wang, X.; Huo, H.; Fan, Q. K.; Wang, J.; Yang, L. M.; Wu, Y. E. Adv. Energy Mater. 2020, 10, 2001709. doi: 10.1002/aenm.202001709
[27]	Yao, D. Z.; Tang, C.; Vasileff, A.; Zhi, X.; Jiao, Y.; Qiao, S. Z. Angew. Chem. Int. Ed. 2021, 60, 18178. doi: 10.1002/anie.202104747
[28]	Ma, W. X.; Bu, J.; Liu, Z. P.; Yan, C.; Yao, Y.; Chang, N. H.; Zhang, H. P.; Wang, T.; Zhang, J. Adv. Funct. Mater. 2020, 31, 2006704. doi: 10.1002/adfm.202006704
[29]	Yang, Q.; Wu, Q. L.; Liu, Y.; Luo, S. P.; Wu, X. T.; Zhao, X. X.; Zou, H. Y.; Long, B. H.; Chen, W.; Liao, Y. J.; Li, L. X.; Shen, P. K.; Duan, L. L.; Quan, Z. W. Adv. Mater. 2020, 32, 2002822.
[30]	Zhao, X. H.; Chen, Q. S.; Zhuo, D. H.; Lu, J.; Xu, Z. N.; Wang, C. M.; Tang, J. X.; Sun, S. G.; Guo, G. C. Electrochim. Acta 2021, 367, 137478. doi: 10.1016/j.electacta.2020.137478
[31]	Zhuo, D. H.; Chen, Q. S.; Zhao, X. H.; Jiang, Y. L.; Lu, J.; Xu, Z. N.; Guo, G. C. J. Mater. Chem. C 2021, 9, 7900. doi: 10.1039/D1TC01766G

富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐^※

Porous Bismuth Nanoflowers Enriched with Lattice Dislocations for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate^※

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 3

参考文献 31

相关文章 15

编辑推荐

相关统计

本文评价

[1]	李珊, 路俊欣, 刘杰, 蒋绿齐, 易文斌. 氟烷基亚磺酸钠盐电化学合成α-氟烷基酮[J]. 化学学报, 2024, 82(2): 110-114.
[2]	刘建川, 李翠艳, 刘耀祖, 王钰杰, 方千荣. 高稳定二维联咔唑sp²碳共轭共价有机框架材料用于高效电催化氧还原^★[J]. 化学学报, 2023, 81(8): 884-890.
[3]	杨贯文, 伍广朋. 模块化双功能有机硼氮和硼磷催化体系的设计及其催化转化^★[J]. 化学学报, 2023, 81(11): 1551-1565.
[4]	杨镇鸿, 干晓娟, 王书哲, 段君元, 翟天佑, 刘友文. 金属性Ni₃N纳米粒子的制备与乙二醇电氧化性能^★[J]. 化学学报, 2023, 81(11): 1471-1477.
[5]	闫绍兵, 焦龙, 何传新, 江海龙. ZIF-67/石墨烯复合物衍生的氮掺杂碳限域Co纳米颗粒用于高效电催化氧还原[J]. 化学学报, 2022, 80(8): 1084-1090.
[6]	何家伟, 焦柳, 程雪怡, 陈光海, 吴强, 王喜章, 杨立军, 胡征. 金属有机框架衍生的空心碳纳米笼的结构调控与锂硫电池性能研究[J]. 化学学报, 2022, 80(7): 896-902.
[7]	王丹, 封波, 张晓昕, 刘亚楠, 裴燕, 乔明华, 宗保宁. 基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂[J]. 化学学报, 2022, 80(6): 772-780.
[8]	应霞薇, 浮建军, 曾敏, 刘文, 张天宇, 沈培康, 张信义. 基于BiOCl-Fe₂O₃@TiO₂介孔复合材料的光电化学合成氨性能研究[J]. 化学学报, 2022, 80(4): 503-509.
[9]	李泽洋, 杨宇森, 卫敏. 二氧化碳还原电催化剂的结构设计及性能研究进展[J]. 化学学报, 2022, 80(2): 199-213.
[10]	安攀, 张庆慧, 杨状, 武佳星, 张佳颖, 王雅君, 李宇明, 姜桂元. 双碳目标下太阳能制氢技术的研究进展[J]. 化学学报, 2022, 80(12): 1629-1642.
[11]	王金格, 周伟, 李佳轶, 丁雅妮, 高继慧. 脉冲电催化的研究进展及性能强化机制[J]. 化学学报, 2022, 80(11): 1555-1568.
[12]	王自陶, 刘耀祖, 王钰杰, 方千荣. 一种新型磺酸修饰的共价有机框架用于二氧化碳吸收和染料吸附[J]. 化学学报, 2022, 80(1): 37-43.
[13]	王旭生, 杨胥, 陈春辉, 李红芳, 黄远标, 曹荣. 石墨烯量子点/铁基金属-有机骨架复合材料高效光催化二氧化碳还原^※[J]. 化学学报, 2022, 80(1): 22-28.
[14]	王瑞兆, 邹云杰, 洪晟, 徐铭楷, 凌岚. Pt_0.01Fe_0.05-g-C₃N₄催化剂高效光热催化二氧化碳还原[J]. 化学学报, 2021, 79(7): 932-940.
[15]	穆春辉, 张艺馨, 寇伟, 徐联宾. 镍氮掺杂有序大孔/介孔碳负载银纳米颗粒用于高效电催化CO₂还原[J]. 化学学报, 2021, 79(7): 925-931.

富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐※

Porous Bismuth Nanoflowers Enriched with Lattice Dislocations for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate※

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 3

参考文献 31

相关文章 15

编辑推荐

相关统计

本文评价

富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐^※

Porous Bismuth Nanoflowers Enriched with Lattice Dislocations for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate^※