甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化

doi:10.1016/S1872-2067(20)63766-4

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2206-2215.DOI: 10.1016/S1872-2067(20)63766-4

甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化

Steffen Cychy^a, Sebastian Lechler^a, Zijian Huang^a, Michael Braun^b, Ann Cathrin Brix^c, Peter Blümler^d, Corina Andronescu^b, Friederike Schmid^d, Wolfgang Schuhmann^c, Martin Muhler^a^,^*()

^a波鸿鲁尔大学化学与生物化学系, 工业化学实验室, 波鸿, 德国
^b杜伊斯堡-埃森大学化学学院, 埃森, 德国
^c波鸿鲁尔大学化学与生物化学系, 分析化学-电化学科学中心, 波鸿, 德国
^d美因茨约翰内斯古腾堡大学物理所, 美因茨, 德国

收稿日期:2020-12-23 接受日期:2020-12-23 出版日期:2021-12-18 发布日期:2021-05-06
通讯作者: Martin Muhler

Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation

Steffen Cychy^a, Sebastian Lechler^a, Zijian Huang^a, Michael Braun^b, Ann Cathrin Brix^c, Peter Blümler^d, Corina Andronescu^b, Friederike Schmid^d, Wolfgang Schuhmann^c, Martin Muhler^a^,^*()

^aLaboratory of Industrial Chemistry, Department of Chemistry and Biochemistry, Ruhr University Bochum, Universitätsstr. 150, D-44801 Bochum, Germany
^bTechnical Chemistry III and CENIDE, Faculty of Chemistry, University of Duisburg-Essen, Universitätsstr. 7, D-45141, Essen, Germany
^cAnalytical Chemistry - Center for Electrochemical Sciences (CES), Faculty of Chemistry and Biochemistry, Ruhr University Bochum, Universitätsstr. 150, D-44801 Bochum, Germany
^dInstitute of Physics, Johannes Gutenberg-University Mainz, Staudingerweg 9, D-55128 Mainz, Germany

Received:2020-12-23 Accepted:2020-12-23 Online:2021-12-18 Published:2021-05-06
Contact: Martin Muhler
About author:* E-mail: muhler@techem.rub.de

摘要/Abstract

摘要：

在碱性甘油电氧化反应中, 利用电化学傅里叶变换衰减全反射谱红外光谱法, 研究了薄膜流动池中滴注硼酸镍催化剂负载量对玻碳电极性能的影响. 连续操作的径向流动池包括一个位于内反射元件上方50 µm的钻孔电极, 可实现红外光谱分析. 这是在确定条件下对电催化剂进行简便和可重复筛选的一个适合的方法, 同时还提供了对复杂反应(如甘油氧化)产物选择性的检测. 通过对泵送电解液进行更耗时的定量高效液相色谱分析, 结果表明, 衰减全反射红外光谱法可快速鉴定产物. 在层流条件下, 水中使用0.1 M甘油和1 M KOH, 流速为5 µL min^-1时, 甘油转化率较高. 转化率和选择性取决于催化剂的负载量, 负载量又决定了催化剂层的厚度和粗糙度. 由于在更粗糙的膜中停留时间更长有利于再吸附和C-C键断裂, 因此当负载量最高达210 µg cm^-2时, 甘油转化率为73%且甲酸选择性接近80%. 当最低负载量为13 µg cm^-2时, 甘油转化率达到63%, 甲酸选择性降至60%, 相应地, C₂物种(如乙醇酸盐)选择性较高, 为8%. 因此, 只有催化剂负载量较低时才能形成几微米厚度范围内的薄膜, 此时才适合进行优质催化剂的筛选.

关键词: 催化剂层厚度, 电催化剂, 硼化镍, 工况下衰减全反射红外光谱, 高效液相色谱, 流动池, 薄膜, 甘油阳极氧化

Abstract:

The influence of the drop-casted nickel boride catalyst loading on glassy carbon electrodes was investigated in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in alkaline glycerol electrooxidation. The continuously operated radial flow cell consisted of a borehole electrode positioned 50 µm above an internal reflection element enabling operando FTIR spectroscopy. It is identified as a suitable tool for facile and reproducible screening of electrocatalysts under well-defined conditions, additionally providing access to the selectivities in complex reaction networks such as glycerol oxidation. The fast product identification by ATR-IR spectroscopy was validated by the more time-consuming quantitative HPLC analysis of the pumped electrolyte. High degrees of glycerol conversion were achieved under the applied laminar flow conditions using 0.1 M glycerol and 1 M KOH in water and a flow rate of 5 µL min^-1. Conversion and selectivity were found to depend on the catalyst loading, which determined the catalyst layer thickness and roughness. The highest loading of 210 µg cm^-2 resulted in 73% conversion and a higher formate selectivity of almost 80%, which is ascribed to longer residence times in rougher films favoring readsorption and C-C bond scission. The lowest loading of 13 µg cm^-2 was sufficient to reach 63% conversion, a lower formate selectivity of 60%, and, correspondingly, higher selectivities of C₂ species such as glycolate amounting to 8%. Thus, only low catalyst loadings resulting in very thin films in the few μm thickness range are suitable for reliable catalyst screening.

Key words: Catalyst layer thicknes, Electrocatalyst, Nickel boride, Operando ATR-IR, High performance liquid chromatography, Flow cell, Thin film, Anodic glycerol oxidation

Steffen Cychy, Sebastian Lechler, Zijian Huang, Michael Braun, Ann Cathrin Brix, Peter Blümler, Corina Andronescu, Friederike Schmid, Wolfgang Schuhmann, Martin Muhler. 甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化[J]. 催化学报, 2021, 42(12): 2206-2215.

Steffen Cychy, Sebastian Lechler, Zijian Huang, Michael Braun, Ann Cathrin Brix, Peter Blümler, Corina Andronescu, Friederike Schmid, Wolfgang Schuhmann, Martin Muhler. Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation[J]. Chinese Journal of Catalysis, 2021, 42(12): 2206-2215.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63766-4

https://www.cjcatal.com/CN/Y2021/V42/I12/2206

图/表 11

Fig. 1. (a) Photograph of the used setup with the homemade lid which enables tilt correction of the BHE over the IRE. (b) Scheme of the BHE placed above the Ge-IRE. By pumping electrolyte through the middle of the BHE, a radial flow profile is obtained between BHE and IRE. The catalyst is immobilized on a glassy carbon ring (black). Formed products and depleted reactants are detected in the evanescent wave above the IRE. In this configuration, a cylindric volume element is formed under the BHE. The relative distance between BHE and IRE is exaggerated for clarity.

Fig. 2. Simulation of the flow conditions in the 50 µm thin electrolyte layer underneath the BHE at a flow rate of 5 µL min-1 calculated with finite elements using COMSOL Multiphysics 5.5. (a) 2D simulation through one half of the BHE. (b) Magnification of the flow profile close to the borehole. The yellow curve indicates the velocity profile in radial direction at a height of 25 µm.

Fig. 3. LSM images of the different loadings on glassy carbon disks with a diameter of 8 mm. The magnified images correspond to areas of 1063 µm times 1418 µm.

Fig. 4. CVs as a function of the different NixB loadings (210, 52, 13 µg cm-2) in 1 M KOH (a) and b)) as well as 0.1 M glycerol/1 M KOH (c) and (d)). (a) 10 cycles recorded as conditioning with 100 mV s-1 between 1.04 to 1.64 V vs. RHE. The following CVs were obtained at lower scan rates of 10 mV s-1 ranging to a higher upper potential of 1.84 V vs. RHE. One scan was recorded in (b), five in (c) and one in (d). The CVs (a) to (c) were recorded at 1600 rpm; (d) was recorded under static conditions.

Fig. 5. Current density response as a function of time to the potential profile where 100 mV potential steps (10 min each) ranging from 1.3 V to 1.8 V vs. RHE were applied intermitted by a 4 min rinsing step at 1.0 V where no GOR is expected. The distance between BHE and IRE was set to 50 µm and a flow rate of 5 µL min-1 was applied. Corresponding spectra are shown in Fig. 6.

Fig. 6. Spectra recorded during the potential step profile shown in Fig. 5. (a) Recorded spectra from 1.3 to 1.8 V vs. RHE for a catalyst loading of 210 µg cm-2, (b) of 52 µg cm-2 and (c) of 13 µg cm-2. Solid lines represent the last spectra during each step (recorded from 8 to 9.5 min during each step) and dashed lines the last spectrum during the rinsing step after the respective elevated potential step (recorded from 2 to 3.5 min during each rinsing step). Positive (upwards pointing) bands are caused by formed species and consumed species (glycerol) are represented by negative bands due to the log(R-1) scale. F is formate, GCol is glycolate, C is carbonate, Ox is oxalate and G is glycerol.

Table 1 Sum of the selectivities for samples 1 and 2 of the different catalyst loadings and difference to 100%.

Sample	Loading µg cm^-1	ΣS_i/%	Δ/%
First	210	96.91	3.09
	52	94.15	5.85
	13	90.26	9.74
Second	210	95.47	4.53
	52	92.82	7.18
	13	88.72	11.27

Fig. 7. Chronoamperometric data obtained for HPLC analysis of electrolyzed 0.1 M glycerol in 1 M KOH electrolyte over NixB at 1.8 V for 2 h. The insert shows a zoom of the first 10 min.

Fig. 8. Conversion of glycerol determined via HPLC analysis of the pumped electrolyte during the chronoamperometric measurements for catalyst loadings of 210, 52 and 13 µg cm-2 shown in Fig. 7 of two different samples obtained for 30 min each. Acquisition started after 1 h pumping time.

Fig. 9. Selectivities for different catalyst loadings in the first and second sample. The inset is a magnification excluding formate.

Fig. 10. Simplified reaction scheme of the GOR representing the complex and interwoven pathway from C3 to C1 species.

参考文献

[1]	S. E. Hosseini, M. A. Wahid, Renew. Sust. Energy Rev., 2016, 57, 850-866.
[2]	H. B. Tao, Y. Xu, X. Huang, J. Chen, L. Pei, J. Zhang, J. G. Chen, B. Liu, Joule, 2019, 3, 1498-1509.
[3]	M. Ayoub, A. Z. Abdullah, Renew. Sust. Energy Rev. 2012, 16, 2671-2686.
[4]	M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, C. Della Pina, Angew. Chem. Int. Ed., 2007, 46, 4434-4440.
[5]	Y. Zhou, Y. Shen, J. Piao, ChemElectroChem, 2018, 5, 1636-1643.
[6]	C. Coutanceau, S. Baranton, WIREs: Energy Environ., 2016, 5, 388-400.
[7]	M. S. E Houache, K. Hughes, E. A. Baranova, Sustain. Energy Fuels, 2019, 3, 1892-1915.
[8]	M. S. Faber, S. Jin, Energy Environ. Sci., 2014, 7, 3519-3542.
[9]	L. Cui, W. Zhang, R. Zheng, J. Liu, Chem. Eur. J., 2020, 26, 11661-11672.
[10]	L. Han, S. Dong, E. Wang, Adv. Mater., 2016, 28, 9266-9291.
[11]	B. Habibi, N. Delnavaz, RSC Adv. 2016, 6, 31797-31806.
[12]	M. T. Bender, X. Yuan, K.-S. Choi, Nat. Commun., 2020, 11, 4594.
[13]	Y. Kwon, Y. Y. Birdja, I. Spanos, P. Rodriguez, M. T. M. Koper, ACS Catal., 2012, 2, 759-764.
[14]	Y. Kwon, T. J. P Hersbach, M. T. M. Koper, Top. Catal., 2014, 57, 1272-1276.
[15]	V. L. Oliveira, C. Morais, K. Servat, T. W. Napporn, G. Tremiliosi-Filho, K. B. Kokoh, J. Electroanal. Chem., 2013, 703, 56-62.
[16]	R. M. Sandrini, J. R. Sempionatto, E. Herrero, J. M. Feliu, J. Souza-Garcia, C. A. Angelucci, Electrochem. Commun., 2018, 86, 149-152.
[17]	J. Schnaidt, M. Heinen, D. Denot, Z. Jusys, R. J. Behm, J. Electroanal. Chem., 2011, 661, 250-264.
[18]	M. Simões, S. Baranton, C. Coutanceau, Appl. Catal. B, 2010, 93, 354-362.
[19]	L. Huang, J.-Y. Sun, S.-H. Cao, M. Zhan, Z.-R. Ni, H.-J. Sun, Z. Chen, Z.-Y. Zhou, E. G. Sorte, Y. J. Tong, S. G. Sun, ACS Catal., 2016, 6, 7686-7695.
[20]	C. Dai, L. Sun, H. Liao, B. Khezri, R. D. Webster, A. C. Fisher, Z. J. Xu, J. Catal., 2017, 356, 14-21.
[21]	Y. Kwon, K. J. P Schouten, M. T. M. Koper, ChemCatChem, 2011, 3, 1176-1185.
[22]	Y. Kwon, M. T. M. Koper, Anal. Chem., 2010, 82, 5420-5424.
[23]	S. Sun, L. Sun, S. Xi, Y. Du, M. U Anu Prathap, Z. Wang, Q. Zhang, A. Fisher, Z. J. Xu, Electrochim. Acta, 2017, 228, 183-194.
[24]	C. Zhu, B. Lan, R.-L. Wei, C.-N. Wang, Y.-Y. Yang, ACS Catal., 2019, 9, 4046-4053.
[25]	J.-T. Li, Z.-Y. Zhou, I. Broadwell, S.-G. Sun, Acc. Chem. Res., 2012, 45, 485-494.
[26]	M. Osawa, in: Handbook of Vibrational Spectroscopy, J. M. Chalmers, P. R. Griffiths, Eds., Wiley, Chichester, 2002.
[27]	Y.-Y. Yang, J. Ren, H.-X. Zhang, Z.-Y. Zhou, S.-G. Sun, W.-B. Cai, Langmuir, 2013, 29, 1709-1716.
[28]	C. Korzeniewski, in: Advances in Electrochemical Sciences and Engineering, R. C. Alkire, D. M. Kolb, J. Lipkowski, P. N. Ross, Eds., Wiley, 2006, 233-268.
[29]	D. Hiltrop, J. Masa, A. J. R Botz, A. Lindner, W. Schuhmann, M. Muhler, Anal. Chem., 2017, 89, 4367-4372.
[30]	S. Cychy, D. Hiltrop, C. Andronescu, M. Muhler, W. Schuhmann, Anal. Chem., 2019, 91, 14323-14331.
[31]	M. Heinen, Y. X. Chen, Z. Jusys, R. J. Behm, Electrochim. Acta, 2007, 52, 5634-5643.
[32]	Y. X. Chen, M. Heinen, Z. Jusys, R. J. Behm, Angew. Chem. Int. Ed., 2006, 45, 981-985.
[33]	V. K. Puthiyapura, W.-F. Lin, A. E. Russell, D. J. L. Brett, C. Hardacre, Top. Catal., 2018, 61, 240-253.
[34]	J. Masa, I. Sinev, H. Mistry, E. Ventosa, M. de La Mata, J. Arbiol, M. Muhler, B. Roldan Cuenya, W. Schuhmann, Adv. Energy Mater., 2017, 7, 1700381.
[35]	N. E. de Souza, J. F. Gomes, G. Tremiliosi-Filho, J. Electroanal. Chem., 2017, 800, 106-113.
[36]	D. Mellmann, P. Sponholz, H. Junge, M. Beller, Chem. Soc. Rev., 2016, 45, 3954-3988.

甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化

Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 11

参考文献

相关文章 15

编辑推荐

Metrics

[1]	周波, 石建巧, 姜一民, 肖磊, 逯宇轩, 董帆, 陈晨, 王特华, 王双印, 邹雨芹. 强化脱氢动力学实现超低电池电压和大电流密度下抗坏血酸电氧化[J]. 催化学报, 2023, 50(7): 372-380.
[2]	欧阳玲, 梁杰, 罗永嵩, 郑冬冬, 孙圣钧, 刘倩, Mohamed S. Hamdy, 孙旭平, 应斌武. 电催化合成氨的研究进展[J]. 催化学报, 2023, 50(7): 6-44.
[3]	李静静, 张锋伟, 詹新雨, 郭河芳, 张涵, 昝文艳, 孙振宇, 张献明. 酞菁镍分子结构的精确设计: 优化电子和空间效应用于CO₂电还原[J]. 催化学报, 2023, 48(5): 117-126.
[4]	张文静, 李静, 魏子栋. 碳基氧还原电催化剂: 机理研究和多孔结构[J]. 催化学报, 2023, 48(5): 15-31.
[5]	吴则星, 高玉肖, 王子璇, 肖卫平, 王新萍, 李彬, 李镇江, 刘晓斌, 马天翼, 王磊. 表面富集的超小铂纳米颗粒耦合缺陷磷化钴用于高效的电催化水分解和柔性锌空气电池[J]. 催化学报, 2023, 46(3): 36-47.
[6]	刘小妮, 刘晓斌, 李彩霞, 杨波, 王磊. 缺陷工程在金属基电池中的研究进展[J]. 催化学报, 2023, 45(2): 27-87.
[7]	逯宇轩, 杨柳, 姜一民, 原甑然, 王双印, 邹雨芹. 局域静电环境工程用于增强电催化生物质转化过程中羟基活性[J]. 催化学报, 2023, 53(10): 153-160.
[8]	乔玉彦, 潘艳秋, 张江威, 王彬, 武婷婷, 范文俊, 曹雨程, Rashid Mehmood, 张飞, 章福祥. 多碳界面工程用于促进NiFe纳米复合电催化剂的产氧反应[J]. 催化学报, 2022, 43(9): 2354-2362.
[9]	崔彤, 翟雪君, 郭莉莉, 迟京起, 张昱, 朱家伟, 孙雪梅, 王磊. 自组装百合花状超低Ru, Ni掺杂的Fe₂O₃用于大电流碱性海水电解双功能电催化[J]. 催化学报, 2022, 43(8): 2202-2211.
[10]	钱秀, 魏艳娇, 孙梦洁, 韩野, 张晓俐, 田健, 邵敏华. 在Ti₃C₂T_x MXene上原位生长2D TiO₂纳米片的异质结构用于改善电催化氮气还原[J]. 催化学报, 2022, 43(7): 1937-1944.
[11]	王慧宁, 关安翔, 张俊波, 米玉莹, 李思, 袁涛涛, 静超, 张丽娟, 张林娟, 郑耿锋. 铜掺杂的羟基氧化镍用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(6): 1478-1484.
[12]	张利利, 蒋苏毓, 马炜, 周震. 铂基催化剂的氧还原反应路径调控[J]. 催化学报, 2022, 43(6): 1433-1443.
[13]	牛慧婷, 夏琛沣, 黄磊, Shahid Zaman, Thandavarayan Maiyalagan, 郭巍, 游波, 夏宝玉. 一维铂基纳米结构氧还原电催化剂的设计与合成[J]. 催化学报, 2022, 43(6): 1459-1472.
[14]	陈晨欣, 何苏祺, Kamran Dastafkan, 邹泽华, 汪庆祥, 赵川. 海胆状NiMoO₄纳米棒阵列作为高效双功能催化剂用于电催化及光伏驱动尿素电解[J]. 催化学报, 2022, 43(5): 1267-1276.
[15]	周波, 李梦雨, 李莹莹, 刘彦伯, 逯宇轩, 李巍, 吴雨洁, 霍甲, 王燕勇, 陶李, 王双印. Co诱导双位点协同效应实现高效肼电催化氧化[J]. 催化学报, 2022, 43(4): 1131-1138.