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

doi:10.6023/A21030104

摘要/Abstract

多组分体系中的协同作用为设计高效的二氧化碳还原电催化剂提供了新的思路. 本工作通过双模板法和化学还原法精心设计制备了大孔/介孔镍氮掺杂碳(Ni-N-OMMC)负载银纳米颗粒复合材料(Ag/Ni-N-OMMC), 用于高效电催化还原CO₂为CO. 此复合材料表现出良好的电催化活性, 在CO₂饱和的0.1 mol•L^–1 KHCO₃电解液中, 电位为–1.0 V (相对于可逆氢电极, RHE)时CO的电流密度(J_CO)高达33.29 mA•cm^–2. 并具有较宽的工作电压范围, 在–0.7~–1.0 V (vs. RHE)下, CO的法拉第效率超过90%. 其优异的电催化性能可能归因于Ag纳米颗粒与具有丰富Ni-N _x活性位点的Ni-N-OMMC载体之间的协同效应, 以及三维互联有序大孔/介孔结构提供的高比表面积和高效的质量/电荷传输.

关键词: 有序大孔/介孔结构, 镍氮共掺杂碳, 双模板合成, 银纳米颗粒, 电催化CO₂还原

Electrocatalytic CO₂ reduction (ECR) into high value-added chemical products has been regarded as an effective strategy to release environmental crisis caused by high concentration of CO₂ in the atmosphere, because of its mild operation conditions and the ability to use renewable energy sources as power. Metal-nitrogen-doped carbon-based nanomaterials have been demonstrated as excellent catalysts for electrochemical reduction of CO₂ due to their high selectivity and low cost. However, it suffers from the problem of low Faradaic efficiency at high current density, which limits their further applications. In addition, the silver-based catalysts have good catalytic activity for the electrochemical reduction of CO₂ to CO, but they can only achieve high selectivity under high overpotentials. The synergistic effect in the multi-component system provides a new idea for the design of efficient electrocatalysts for carbon dioxide reduction. Herein, we first elaborately design and prepare an ordered macro-/mesoporous nickel-nitrogen-doped carbon (Ni-N-OMMC) supported silver nanoparticles composite (Ag/Ni-N-OMMC) by the use of silica colloidal crystal as the hard template and triblock copolymer Pluronic F127 as the mesoporous structure-directing agent, and study the electrocatalytic CO₂ reduction performance. Due to the confinement effect, the small silver nanoparticles are successfully loaded on the Ni-N-OMMC support by in-situ chemical reduction. Compared to Ni-N-OMMC, Ag/Ni-N-OMMC exhibits better electrocatalytic activity. The Faradaic efficiency of CO is as high as 98.7% when the potential is –0.7 V vs. reversible hydrogen electrode (RHE) in 0.1 mol•L^–1 KHCO₃ electrolyte. Moreover, Ag/Ni-N-OMMC has a wide operating voltage range with the Faradaic efficiency of CO over 90% at –0.7~ –1.0 V, and shows a high current density of CO (33.29 mA•cm^–2) at –1.0 V. The excellent ECR performance of Ag/Ni-N-OMMC may be attributed to the synergistic effect between Ag nanoparticles and the Ni-N-OMMC support with abundant Ni-N _x active sites, as well as the high specific surface area and efficient mass/charge transfer provided by the three-dimensional interconnected ordered macro-/mesoporous structure. This study provides an idea for future design and preparation of metal-carbon composite electrocatalysts with high activity and selectivity.

Key words: ordered macro-/mesoporous structure, Ni-N-doped carbon, dual-templating synthesis, Ag nanoparticle, electrocatalytic CO₂ reduction

引用此文

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.

Chunhui Mu, Yixin Zhang, Wei Kou, Lianbin Xu. Nickel-Nitrogen-Doped Ordered Macro-/Mesoporous Carbon Supported Ag Nanoparticles for Efficient Electrocatalytic CO₂ Reduction[J]. Acta Chimica Sinica, 2021, 79(7): 925-931.

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

分享此文

图/表 5

图1. Ag/Ni-N-OMMC的制备流程

Figure 1. Schematic of the synthesis of Ag/Ni-N-OMMC

图2. (a) SiO2 opal和(b) Ni-N-OMMC (插图: 更高放大倍率)的SEM图; (c) Ni-N-OMMC (插图: 更高放大倍率)和(d) Ag/Ni-N-OMMC的TEM图(插图: Ag纳米颗粒的HR-TEM图); (e) Ag/Ni-N-OMMC中C、N、Ni和Ag的 EDS mapping元素分布图

Figure 2. SEM images of (a) SiO2 opal and (b) Ni-N-OMMC (inset: at a higher magnification); TEM images of (c) Ni-N-OMMC (inset: at a higher magnification) and (d) Ag/Ni-N-OMMC (inset: HR-TEM image of Ag nanoparticles); (e) EDS mapping images of C, N, Ni and Ag elements of Ag/Ni-N-OMMC

图3. Ni-N-OMMC, Ag/Ni-N-OMMC, Ag/OMMC和Ag/XC-72R的广角XRD图谱

Figure 3. Wide-angle XRD patterns of Ni-N-OMMC, Ag/Ni-N-OMMC, Ag/OMMC and Ag/XC-72R

图4. Ag/Ni-N-OMMC的(a) XPS总谱图; (b) N 1s, (c) Ni 2p和(d) Ag 3d的高分辨图谱

Figure 4. (a) XPS survey spectrum; high-resolution XPS spectra of (b) N 1s, (c) Ni 2p and (d) Ag 3d of Ag/Ni-N-OMMC

图5. Ag/Ni-N-OMMC, Ni-N-OMMC, Ag/OMMC和Ag/XC-72R的ECR性能测试. (a)在CO2饱和的0.1 mol•L–1 KHCO3溶液中的LSV曲线(插图: Ag/Ni-N-OMMC在N2和CO2饱和的0.1 mol•L–1 KHCO3溶液中的LSV曲线), 扫速10 mV•s–1; (b)不同电位下CO的法拉第效率; (c)不同电位下CO的分电流密度; (d) CO的Tafel斜率; (e)电流密度与扫速的关系曲线; (f) Ag/Ni-N-OMMC在–0.7 V vs. RHE的稳定性测试

Figure 5. ECR performances for Ag/Ni-N-OMMC, Ni-N-OMMC, Ag/OMMC and Ag/XC-72R. (a) LSV curves in the CO2-saturated 0.1 mol•L–1 KHCO3 solution (inset: LSV curves for Ag/Ni-N-OMMC measured in N2- and CO2-saturated 0.1 mol•L–1 KHCO3 solutions) with 10 mV•s–1; (b) CO Faradaic efficiency at different potentials; (c) CO current density at different potentials; (d) Tafel plots for CO; (e) correlation curves between current density and sweep speed; (f) durability test of Ag/Ni-N-OMMC at a constant potential of –0.7 V vs. RHE

参考文献 41

[1]	Xiao, J.; Gao, M.-R.; Liu, S.-B.; Luo, J.-L. ACS Appl. Mater. Interfaces 2020, 12, 31431. doi: 10.1021/acsami.0c06891
[2]	Jin, H.-D.; Xiong, L.-K.; Zhang, X.; Lian, Y.-B.; Chen, S.; Lu, Y.-T.; Deng, Z.; Peng, Y. Acta Phys.-Chim. Sin. 2021, 37, 2006017. (in Chinese)
	(金惠东, 熊力堃, 张想, 连跃彬, 陈思, 陆永涛, 邓昭, 彭扬, 物理化学学报, 2021, 37, 2006017.)
[3]	Liu, S.-B.; Lu, X.-F.; Xiao, J.; Wang, X.; Lou, X.-W. Angew. Chem., Int. Ed. 2019, 58, 13828. doi: 10.1002/anie.v58.39
[4]	Wang, Y.-L.; Tian, Y.; Lang, Z.-L.; Guan, W.; Yan, L.-K. J. Mater. Chem. A 2018, 6, 21056. doi: 10.1039/C8TA07352J
[5]	Zhou, P.; Chao, Y.-G.; Lv, F.; Lai, J.-P.; Wang, K.; Guo, S.-J. Sci. Bull. 2020, 65, 720. doi: 10.1016/j.scib.2019.12.025
[6]	Shi, J.-F.; Jiang, Y.-J.; Jiang, Z.-Y.; Wang, X.-Y.; Wang, X.-L.; Zhang, S.-H.; Han, P.-P.; Yang, C. Chem. Soc. Rev. 2015, 44, 5981. doi: 10.1039/C5CS00182J
[7]	Du, C.-Y.; Chen, Y.-F. Acta Chim. Sinica 2020, 78, 938. (in Chinese) doi: 10.6023/A20060268
	(杜重阳, 陈耀峰, 化学学报, 2020, 78, 938.) doi: 10.6023/A20060268
[8]	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
[9]	Ma, Y.-N.; Shi, R.; Zhang, T.-R. Acta Chim. Sinica 2021, 79, 369. (in Chinese) doi: 10.6023/A20110540
	(马一宁, 施润, 张铁锐, 化学学报, 2021, 79, 369.) doi: 10.6023/A20110540
[10]	Bushuyev, O. S.; De Luna, P.; Dinh, C. T.; Tao, L.; Saur, G.; van de Lagemaat, J.; Kelley, S. O.; Sargent, E. H. Joule 2018, 2, 825. doi: 10.1016/j.joule.2017.09.003
[11]	Peng, Z.-K.; Ding, H.-M.; Chen, R.-F.; Gao, C.; Wang, C. Acta Chim. Sinica 2019, 77, 681. (in Chinese) doi: 10.6023/A19040118
	(彭正康, 丁慧敏, 陈如凡, 高超, 汪成, 化学学报, 2019, 77, 681.) doi: 10.6023/A19040118
[12]	Wang, Y.-X.; Cao, L.; Libretto, N. J.; Li, X.; Li, C.-Y.; Wan, Y.-D.; He, C.; Lee, J.; Gregg, J.; Zong, H.; Su, D.; Miller, J. T.; Mueller, T.; Wang, C. J. Am. Chem. Soc. 2019, 141, 16635. doi: 10.1021/jacs.9b05766
[13]	Zhang, W.-J.; Hu, Y.; Ma, L.-B.; Zhu, G.-Y.; Wang, Y.-R.; Xue, X.-L.; Chen, R.-P.; Yang, S.-Y.; Jin, Z. Adv. Sci. 2018, 5, 1700275. doi: 10.1002/advs.201700275
[14]	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
[15]	Wang, W.; Shang, L.; Chang, G.-J.; Tan, C.-Y.; Shi, R.; Zhao, Y.-X.; Waterhouse, G.; Yang, D.-J.; Zhang, T.-R. Adv. Mater. 2019, 31, 1808276. doi: 10.1002/adma.v31.19
[16]	Gu, J.; Hsu, C. S.; Bai, L.-C.; Chen, H.-M.; Hu, X.-L. Science 2019, 364, 1091. doi: 10.1126/science.aaw7515
[17]	Yan, C.-C.; Li, H.-B.; Ye, Y.-F.; Wu, H.-H.; Cai, F.; Si, R.; Xiao, J.-P.; Miao, S.; Xie, S.-H.; Yang, F.; Li, Y.-S.; Wang, G.-X.; Bao, X.-H. Energy Environ. Sci. 2018, 11, 1204. doi: 10.1039/C8EE00133B
[18]	Xu, C.-C.; Zhi, X.; Vasileff, A.; Wang, D.; Jin, B.; Jiao, Y.; Zheng, Y.; Qiao, S.-Z. Small Struct. 2021, 2, 2000058. doi: 10.1002/sstr.v2.1
[19]	Ju, W.; Bagger, A.; Hao, G.-P.; Varela, A. S.; Sinev, I.; Bon, V.; Cuenya, B. R.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Nat. Commun. 2017, 8, 944. doi: 10.1038/s41467-017-01035-z
[20]	Jiang, K.; Siahrostami, S.; Zheng, T.-T.; Hu, Y.-F.; Hwang, S.; Stavitski, E.; Peng, Y.-D.; Dynes, J.; Gangisetty, M.; Su, D.; Attenkofer, K.; Wang, H.-T. Energy Environ. Sci. 2018, 11, 893. doi: 10.1039/C7EE03245E
[21]	Zhang, B.; Zhao, T.-J.; Feng, W.-J.; Liu, Y.-X.; Wang, H.-H.; Su, H.; Lv, L.-B.; Li, X.-H.; Chen, J.-S. Nano Res. 2018, 11, 2450. doi: 10.1007/s12274-017-1866-y
[22]	Huang, X.-X.; Ma, Y.-J.; Zhi, L.-J. Acta Phys.-Chim. Sin. 2021, 37, 2011050. (in Chinese)
	(黄小雄, 马英杰, 智林杰, 物理化学学报, 2021, 37, 2011050.)
[23]	Zhao, C.-M.; Dai, X.-Y.; Yao, T.; Chen, W.-X.; Wang, X.-Q.; Wang, J.; Yang, J.; Wei, S.-Q.; Wu, Y.-E.; Li, Y.-D. J. Am. Chem. Soc. 2017, 139, 8078. doi: 10.1021/jacs.7b02736
[24]	Sun, M.-H.; Huang, S.-Z.; Chen, L.-H.; Li, Y.; Yang, X.-Y.; Yuan, Z.-Y.; Su, B.-L. Chem. Soc. Rev. 2016, 45, 3479. doi: 10.1039/C6CS00135A
[25]	Kou, W.; Zhang, Y.-X.; Dong, J.; Mu, C.-H.; Xu, L.-B. ACS Appl. Energy Mater. 2020, 3, 1875. doi: 10.1021/acsaem.9b02324
[26]	Shi, R.; Guo, J.-H.; Zhang, X.-R.; Waterhouse, G.; Han, Z.-J.; Zhao, Y.-X.; Shang, L.; Zhou, C.; Jiang, L.; Zhang, T.-R. Nat. Commun. 2020, 11, 3028. doi: 10.1038/s41467-020-16847-9
[27]	Deng, W.-Y.; Zhang, L.; Dong, H.; Chang, X.-X.; Wang, T.; Gong, J.-L. Chem. Sci. 2018, 9, 6599. doi: 10.1039/C8SC02576B
[28]	Gao, D.-F.; Zhou, H.; Wang, J.; Miao, S.; Yang, F.; Wang, G.-X.; Wang, J.-G.; Bao, X.-H. J. Am. Chem. Soc. 2015, 137, 4288. doi: 10.1021/jacs.5b00046
[29]	Back, S.; Yeom, M. S.; Jung, Y. ACS Catal. 2015, 5, 5089. doi: 10.1021/acscatal.5b00462
[30]	Salehi-Khojin, A.; Jhong, H. R. M.; Rosen, B. A.; Zhu, W.; Ma, S.; Kenis, P. J. A.; Masel, R. I. J. Phys. Chem. C 2013, 117, 1627. doi: 10.1021/jp310509z
[31]	Liu, H.-J.; Cui, W.-J.; Jin, L.-H.; Wang, C.-X.; Xia, Y.-Y. J. Mater. Chem. 2009, 19, 3661. doi: 10.1039/b819820a
[32]	Fang, Y.-Y.; Dai, W.; Chen, L.; Ma, N. Mater. Lett. 2016, 174, 246. doi: 10.1016/j.matlet.2016.02.086
[33]	Sun, T.-T.; Dong, J.; Huang, Y.; Ran, W.; Chen, J.-F.; Xu, L.-B. J. Mater. Chem. A 2018, 6, 12751. doi: 10.1039/C8TA03672A
[34]	Wu, J.-J.; Liu, M.-J.; Sharma, P.-P.; Yadav, R. M.; Ma, L.-L.; Yang, Y.-C.; Zou, X.-L.; Zhou, X.-D.; Vajtai, R.; Yakobson, B. I.; Lou, J.; Ajayan, P. M. Nano Lett. 2016, 16, 466. doi: 10.1021/acs.nanolett.5b04123
[35]	Varela, A. S.; Ju, W.; Bagger, A.; Franco, P.; Rossmeisl, J.; Strasser, P. ACS Catal. 2019, 9, 7270. doi: 10.1021/acscatal.9b01405
[36]	Bokare, A. D.; Chikate, R. C.; Rode, C. V.; Paknikar, K. M. Appl. Catal., B 2008, 79, 270. doi: 10.1016/j.apcatb.2007.10.033
[37]	Zhang, H.; Wang, G.; Chen, D.; Lv, X.-J.; Li, J.-H. Chem. Mater. 2008, 20, 6543. doi: 10.1021/cm801796q
[38]	Pan, F.-P.; Li, B.-Y.; Deng, W.; Du, Z.-C.; Gang, Y.; Wang, G.-F.; Li, Y. Appl. Catal., B 2019, 252, 240. doi: 10.1016/j.apcatb.2019.04.025
[39]	Gao, S.; Lin, Y.; Jiao, X.-C.; Sun, Y.-F.; Luo, Q.-Q.; Zhang, W.-H.; Li, D.-Q.; Yang, J.-L.; Xie, Y. Nature 2016, 529, 68. doi: 10.1038/nature16455
[40]	Liu, S.; Yang, H.-B.; Huang, X.; Liu, L.-H.; Cai, W.-Z.; Gao, J.-J.; Li, X.-N.; Zhang, T.; Huang, Y.-Q.; Liu, B. Adv. Funct. Mater. 2018, 28, 1800499. doi: 10.1002/adfm.v28.21
[41]	Lu, P.-L.; Yang, Y.-J.; Yao, J.-N.; Wang, M.; Dipazir, S.; Yuan, M.-L.; Zhang, J.-X.; Wang, X.; Xie, Z.-J.; Zhang, G.-J. Appl. Catal., B 2019, 241, 113.

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

Nickel-Nitrogen-Doped Ordered Macro-/Mesoporous Carbon Supported Ag Nanoparticles for Efficient Electrocatalytic CO₂ Reduction

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 5

参考文献 41

相关文章 4

编辑推荐

相关统计

本文评价

[1]	陈敬煌, 孟天, 武烈, 石恒冲, 杨帆, 孙健, 杨秀荣. AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究^※[J]. 化学学报, 2022, 80(2): 110-115.
[2]	李冉, 卢艳莹, 雷凯翔, 李福军, 程方益, 陈军. 放电态Li-AgVO₃一次电池作为可充Li-O₂电池再利用研究[J]. 化学学报, 2017, 75(2): 199-205.
[3]	白硕,鲁从华,曹维孝. 重氮树脂与银纳米颗粒自组装膜的图像化[J]. 化学学报, 2005, 63(9): 866-868.
[4]	李国平, 罗运军, 谭惠民. 以树形分子为模板制备银纳米颗粒[J]. 化学学报, 2004, 62(12): 1158-1161.