碳布负载的高分散CoP<sub><i>x</i></sub>纳米粒子及其甲醇电催化氧化反应性能的研究

ZHANG Jian-yuan; XING Shuang-feng; ZHAO Shi-chao; XIONG Mi; ZHANG Bian-qin; TONG Xi-li; QIN Yong; GAO Zhe

doi:10.1016/S1872-5813(22)60040-9

碳布负载的高分散CoP_x纳米粒子及其甲醇电催化氧化反应性能的研究

doi: 10.1016/S1872-5813(22)60040-9

张见远^{1, 2},
邢双凤^{1, 2},
赵世超¹,
熊咪^{1, 2},
张变琴^{1, 2},
童希立¹,
覃勇¹,
高哲^1, ,

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学材料与光电研究中心, 北京 100049

详细信息

中图分类号: O643.3
计量
- 文章访问数: 2762
- HTML全文浏览量: 59
- PDF下载量: 61
- 被引次数: 0
出版历程
- 收稿日期: 2022-03-04
- 修回日期: 2022-03-25
- 录用日期: 2022-03-25
- 网络出版日期: 2022-06-22
- 刊出日期: 2022-10-31

Highly dispersed CoP_x nanoparticles supported on carbon cloth for the enhanced catalytic performance of methanol electro-oxidation

ZHANG Jian-yuan^{1, 2},
XING Shuang-feng^{1, 2},
ZHAO Shi-chao¹,
XIONG Mi^{1, 2},
ZHANG Bian-qin^{1, 2},
TONG Xi-li¹,
QIN Yong¹,
GAO Zhe^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Key R&D Program of China (2020YFA0210902 and 2017YFA0700101), National Natural Science Foundation of China (U1932131 and U1832208), National Science Fund for Distinguished Young Scholars (21825204), and Youth Innovation Promotion Association of the Chinese Academy of Sciences (2018208).

More Information

Corresponding author: E-mail: gaozhe@sxicc.ac.cn

摘要

摘要: 直接甲醇燃料电池（DMFC）是一种有潜力的商用燃料电池技术，目前贵金属阳极材料昂贵的价格阻碍其发展。开发分散均匀粒径分布窄的金属磷化物催化剂仍然是一个挑战。本研究通过原子层沉积法（ALD）在碳布上沉积CoO_x，然后经过磷化处理获得CoP_x。通过改变ALD臭氧脉冲（ALD-O₃）的循环数，调控CoO_x（ALD-CoO_x）在碳布上的成核生长方式，获得粒径小、分布均匀的CoP_x纳米粒子。经过优化后的CoP_x纳米催化剂（CoP_x/40-CC）在碱性溶液中对甲醇电催化氧化反应表现出优异的活性（153 mA/cm²），高于浸渍法制备的催化剂（Imp-CoP_x/CC），尽管CoP_x/40-CC的CoP_x负载量低于Imp-CoP_x/CC。结果表明，甲醇电催化氧化过程中的电子转移和传质动力学得到了提高，这得益于CoP_x较小的粒径和均匀的分布。
- 原子层沉积 /
- 磷化钴纳米粒子 /
- 甲醇电催化氧化
Abstract: Direct methanol fuel cell (DMFC) is a potential commercial fuel cell technology that is presently hindered by the expensive noble metal materials of the anode. Developing a method to obtain a uniformly dispersed metal phosphide catalyst with narrow size distribution is still a challenge. In this work, cobalt oxide was deposited on carbon cloth (CC) through atomic layer deposition (ALD), then cobalt phosphide was obtained after the phosphorization process. By changing the number of ALD-based ozone pulses (ALD-O₃) for CC, the nucleation and growth modes of cobalt oxide (ALD-CoO_x) on the CC were regulated, and CoP_x nanoparticles with small particle size and uniform distribution were obtained. The optimized CoP_x-based catalyst with 40 cycles of ALD-O₃ treatment (CoP_x/40-CC) exhibits excellent activity (153 mA/cm²) toward methanol electrocatalytic oxidation reaction in the alkaline solution, which is higher than the catalyst prepared by impregnation (Imp-CoP_x/CC), although the CoP_x loading of CoP_x/40-CC is lower than that of Imp-CoP_x/CC. The results indicate that the enhanced activity benefits from the small particle size and the uniform CoP_x distribution, which promote the electron-transfer and mass transport kinetics of the methanol electro-oxidation process.
- atomic layer deposition /
- cobalt phosphide nanoparticles /
- methanol electrocatalytic oxidation reaction

HTML全文

FIG. 1924. FIG. 1924.

下载: 全尺寸图片幻灯片

Figure 1 Schematic illustration of the catalysts prepared by ALD

下载: 全尺寸图片幻灯片

Figure 2 TEM images of (a) CoO_x/10-CC, (b) CoO_x/40-CC, (c) CoO_x/75-CC, (e) CoP_x/10-CC, (f) CoP_x/40-CC, and (g) CoP_x/75-CC, where the inset shows the nanoparticle size statistics; HRTEM images of (d) CoO_x/40-CC, and (h) CoP_x/40-CC

下载: 全尺寸图片幻灯片

Figure 3 TEM images of (a) Imp-CoO_x/CC and (b) Imp-CoP_x/CC

下载: 全尺寸图片幻灯片

Figure 4 XRD patterns of CoP_x/10-CC, CoP_x/40-CC, CoP_x/75-CC, and Imp-CoP_x/CC

下载: 全尺寸图片幻灯片

Figure 5 XPS (a) Co 2p and (b) P 2p spectra of CoP_x/10-CC, CoP_x/40-CC, CoP_x/75-CC, and Imp-CoP_x/CC

下载: 全尺寸图片幻灯片

Figure 6 (a) CVs, (b) bar graph(@1.7 V vs RHE), and (c) EIS curves of CoP_x/n-CC and Imp-CoP_x/CC for MOR in 1 mol/L KOH + 1 mol/L methanol, (d) Tafel curves and (g) chronoamperometric (CA) results of CoP_x/10-CC, CoP_x/40-CC, CoP_x/75-CC, and Imp-CoP_x/CC, (e) LSV of CoP_x/40-CC in 1 mol/L KOH, with and without 1 mol/L methanol, (f) CV curves of CoP_x/40-CC in 1 mol/L KOH +1 mol/L CH₃OH solution at different scanning rates (10–200 mV/s), where the inset shows the proportionality of current density (@1.7 V vs RHE) vs the square root of the scan rate, (h) CVs and (i) bar graph (@1.7 V vs RHE) of nCoP_x/40-CC and Imp-CoP_x/CC for MOR in 1 mol/L KOH + 1 mol/L methanol

下载: 全尺寸图片幻灯片

Table 1 Comparison of the MOR performance of CoP_x/40-CC with those of other catalysts reported in the literatures.

Electrocatalyst	Electrolyte solution	Current density at 1.7 V vs RHE/(mA·cm⁻²)	Potential at 10 mA/cm² /V	Reference
CoP_x/40-CC	1 mol/L KOH + 1 mol/L methanol	153	1.39	this work
CoP_x hollow spheres	1 mol/L KOH + 1 mol/L methanol	31	1.62	[19]
CoP nanoflowers	1 mol/L KOH + 1 mol/L methanol		1.59	[34]
Hollow CoP OCHs	1 mol/L KOH + 1 mol/L methanol		1.37	[35]
Porous CoP NSs	1 mol/L KOH + 1 mol/L methanol		1.42	[35]
Co₃(PO4)₂ nanosphere	1 mol/L KOH + 1 mol/L methanol	146		[36]

下载: 导出CSV

参考文献(37)

[1]	DEBE M K. Electrocatalyst approaches and challenges for automotive fuel cells[J]. Nature,2012,486(7401):43−51. doi: 10.1038/nature11115
[2]	KAKATI N, MAITI J, LEE S H, JEE S H, VISWANATHAN B, YOON Y S. Anode catalysts for direct methanol fuel cells in acidic media: do we have any alternative for Pt or Pt-Ru?[J]. Chem Rev,2014,114(24):12397−12429. doi: 10.1021/cr400389f
[3]	LI M, DUANMU K, WAN C, CHENG T, ZHANG L, DAI S, CHEN W, ZHAO Z, LI P, FEI H, ZHU Y, YU R, LUO J, ZANG K, LIN Z, DING M, HUANG J, SUN H, GUO J, PAN X, GODDARD W A, SAUTET P, HUANG Y, DUAN X. Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis[J]. Nat Catal,2019,2(6):495−503. doi: 10.1038/s41929-019-0279-6
[4]	LI H H, ZHAO S, GONG M, CUI C H, HE D, LIANG H W, WU L, YU S H. Ultrathin PtPdTe nanowires as superior catalysts for methanol electrooxidation[J]. Angew Chem Int Ed,2013,52(29):7472−7476. doi: 10.1002/anie.201302090
[5]	HUANG H, YANG S, VAJTAI R, WANG X, AJAYAN P M. Pt-decorated 3D architectures built from graphene and graphitic carbon nitride nanosheets as efficient methanol oxidation catalysts[J]. Adv Mater,2014,26(30):5160−5165. doi: 10.1002/adma.201401877
[6]	CHEN Q, YANG Y, CAO Z, KUANG Q, DU G, JIANG Y, XIE Z, ZHENG L. Excavated cubic platinum-tin alloy nanocrystals constructed from ultrathin nanosheets with enhanced electrocatalytic activity[J]. Angew Chem Int Ed,2016,55(31):9021−9025. doi: 10.1002/anie.201602592
[7]	XUE S, DENG W, YANG F, YANG J, AMIINU I S, HE D, TANG H, MU S. Hexapod PtRuCu nanocrystalline alloy for highly efficient and stable methanol oxidation[J]. ACS Catal,2018,8(8):7578−7584. doi: 10.1021/acscatal.8b00366
[8]	ZHAO X, YIN M, MA L, LIANG L, LIU C, LIAO J, LU T, XING W. Recent advances in catalysts for direct methanol fuel cells[J]. Energy Environ Sci,2011,4(8):2736−2753. doi: 10.1039/c1ee01307f
[9]	ZHAI M, CHEN F, WU N, GUO R, ZHANG X, HU T, MA M. Porous layered cobalt nanocrystal/nitrogen-doped carbon composites as efficient and CO-resistant electrocatalysts for methanol oxidation reaction[J]. Appl Surf Sci,2021,545:149016. doi: 10.1016/j.apsusc.2021.149016
[10]	YANG W, YANG X, JIA J, HOU C, GAO H, MAO Y, WANG C, LIN J, LUO X. Oxygen vacancies confined in ultrathin nickel oxide nanosheets for enhanced electrocatalytic methanol oxidation[J]. Appl Catal B: Environ,2019,244:1096−1102. doi: 10.1016/j.apcatb.2018.12.038
[11]	CUI X, GUO W, ZHOU M, YANG Y, LI Y, XIAO P, ZHANG Y, ZHANG X. Promoting effect of Co in Ni_mCo_n (m + n = 4) bimetallic electrocatalysts for methanol oxidation reaction[J]. ACS Appl Mater Inter,2015,7(1):493−503. doi: 10.1021/am506554b
[12]	PEI Y, CHENG Y, CHEN J, SMITH W, DONG P, AJAYAN P M, YE M, SHEN J. Recent developments of transition metal phosphides as catalysts in the energy conversion field[J]. J Mater Chem A,2018,6(46):23220−23243. doi: 10.1039/C8TA09454C
[13]	SHI Y, ZHANG B. Recent advances in transition metal phosphide nanomaterials: Synthesis and applications in hydrogen evolution reaction[J]. Chem Soc Rev,2016,45(6):1529−1541. doi: 10.1039/C5CS00434A
[14]	WALCARIUS A. Mesoporous materials and electrochemistry[J]. Chem Soc Rev,2013,42(9):4098−4140. doi: 10.1039/c2cs35322a
[15]	TONG X, QIN Y, GUO X, MOUTANABBIR O, AO X, PIPPEL E, ZHANG L, KNEZ M. Enhanced catalytic activity for methanol electro-oxidation of uniformly dispersed nickel oxide nanoparticles-carbon nanotube hybrid materials[J]. Small,2012,8(22):3390−3395. doi: 10.1002/smll.201200839
[16]	HUANG L, ZHANG X, WANG Q, HAN Y, FANG Y, DONG S. Shape-control of Pt-Ru nanocrystals: Tuning surface structure for enhanced electrocatalytic methanol oxidation[J]. J Am Chem Soc,2018,140(3):1142−1147. doi: 10.1021/jacs.7b12353
[17]	TANG C, ZHANG R, LU W, HE L, JIANG X, ASIRI A M, SUN X. Fe-Doped CoP nanoarray: A monolithic multifunctional catalyst for highly efficient hydrogen generation[J]. Adv Mater,2017,29(2):1602441. doi: 10.1002/adma.201602441
[18]	LIU D, LU W, WANG K, DU G, ASIRI A M, LU Q, SUN X. Cobalt phosphide nanowall array as an efficient 3D catalyst electrode for methanol electro-oxidation[J]. Nanotechnology,2016,27(44):44LT02. doi: 10.1088/0957-4484/27/44/44LT02
[19]	CHEN S, YANG X, TONG X, ZHANG F, ZOU H, QIAO Y, DONG M, WANG J, FAN W. Design of 3D hollow porous heterogeneous nickel-cobalt phosphides for synergistically enhancing catalytic performance for electrooxidation of methanol[J]. ACS Appl Mater Inter,2020,12(31):34971−34979. doi: 10.1021/acsami.0c08912
[20]	GAO Z, WANG G, LEI T, LV Z, XIONG M, WANG L, XING S, MA J, JIANG Z, QIN Y. Enhanced hydrogen generation by reverse spillover effects over bicomponent catalysts[J]. Nat Commun,2022,13(1):118. doi: 10.1038/s41467-021-27785-5
[21]	GAO Z, DONG M, WANG G, SHENG P, WU Z, YANG H, ZHANG B, WANG G, WANG J, QIN Y. Multiply confined nickel nanocatalysts produced by atomic layer deposition for hydrogenation reactions[J]. Angew Chem Int Ed,2015,54(31):9006−9010. doi: 10.1002/anie.201503749
[22]	ZHANG J, GAO Z, WANG S, WANG G, GAO X, ZHANG B, XING S, ZHAO S, QIN Y. Origin of synergistic effects in bicomponent cobalt oxide-platinum catalysts for selective hydrogenation reaction[J]. Nat Commun,2019,10(1):4166. doi: 10.1038/s41467-019-11970-8
[23]	GAO Z, QIN Y. Design and properties of confined nanocatalysts by atomic layer deposition[J]. Acc Chem Res,2017,50(9):2309−2316. doi: 10.1021/acs.accounts.7b00266
[24]	YANG H, ZHANG B, ZHANG B, GAO Z, QIN Y. N-doped carbon modified Pt/CNTs synthesized by atomic layer deposition with enhanced activity and stability for methanol electrooxidation[J]. Chin J Catal,2018,39(6):1038−1043. doi: 10.1016/S1872-2067(18)63066-9
[25]	MARICHY C, BECHELANY M, PINNA N. Atomic layer deposition of nanostructured materials for energy and environmental applications[J]. Adv Mater,2012,24(8):1017−1032. doi: 10.1002/adma.201104129
[26]	YANG H, CHEN Y, QIN Y. Application of atomic layer deposition in fabricating high-efficiency electrocatalysts[J]. Chin J Catal,2020,41(2):227−241. doi: 10.1016/S1872-2067(19)63440-6
[27]	XING S, GAO Z, ZHAO S, XIONG M, WANG P, ZHANG J, WANG S, WANG G, QIN Y. Amphiphilic confined Pt-based nanocatalysts produced by atomic layer deposition with enhanced catalytic performance for biphasic reactions[J]. Green Chem,2021,23(20):8116−8123. doi: 10.1039/D1GC02261J
[28]	XIONG M, GAO Z, ZHAO P, WANG G, YAN W, XING S, WANG P, MA J, JIANG Z, LIU X, MA J, XU J, QIN Y. In situ tuning of electronic structure of catalysts using controllable hydrogen spillover for enhanced selectivity[J]. Nat Commun,2020,11(1):4773. doi: 10.1038/s41467-020-18567-6
[29]	WEN Y, CAI J, ZHANG J, YANG J, SHI L, CAO K, CHEN R, SHAN B. Edge-selective growth of MCp₂ (M = Fe, Co, and Ni) precursors on Pt nanoparticles in atomic layer deposition: A combined theoretical and experimental study[J]. Chem Mater,2018,31(1):101−111.
[30]	ZHENG Y, QIAO J, HU J, SONG F, HUO D, YUAN J, SHEN J, NIU L, WANG A. PtIr alloy nanowire assembly on carbon cloth as advanced anode catalysts for methanol oxidation[J]. Int J Hydrog Energy,2019,44(36):20336−20344. doi: 10.1016/j.ijhydene.2019.05.218
[31]	ZHOU X, LI X, PRINS R, LV J, WANG A, SHENG Q. Hydrodesulfurization of dibenzothiophene and its hydrogenated intermediates over bulk CoP and Co₂P catalysts with stoichiometric P/Co ratios[J]. J Catal,2021,394:167−180. doi: 10.1016/j.jcat.2020.08.030
[32]	LONI E, SIADATI M H, SHOKUHFAR A. Mesoporous cobalt-cobalt phosphide electrocatalyst for water splitting[J]. Mater Today Energy,2020,16:100398. doi: 10.1016/j.mtener.2020.100398
[33]	SUN X, LIU C, ZHANG P, GONG LWANG M. Interface-engineered silicon photocathodes with a NiCoP catalyst-modified TiO₂ nanorod array outlayer for photoelectrochemical hydrogen production in alkaline solution[J]. J Power Sources,2021,484:229272.
[34]	ZHAO F, YANG H, QIN K, CUI GLIU Q. Three-dimensional heterogeneous copper cobalt phosphides Nanoflowers for enhancing catalytic performance for electro-oxidation of methanol[J]. J Chin Inst Chem Eng,2021,126:244−251.
[35]	XU J, LIU Y, LI J, AMORIM I, ZHANG B, XIONG D, ZHANG N, THALLURI S M, SOUSA J P SLIU L. Hollow cobalt phosphide octahedral pre-catalysts with exceptionally high intrinsic catalytic activity for electro-oxidation of water and methanol[J]. J Mater Chem A,2018,6(42):20646−20652. doi: 10.1039/C8TA07958G
[36]	ARUNACHALAM P, SHADDAD M, ALAMOUDI A, GHANEM MAL-MAYOUF A. Microwave-assisted synthesis of Co₃(PO4)₂ nanospheres for electrocatalytic oxidation of methanol in alkaline media[J]. Catalysts, 2017, 7 (12): 119.
[37]	YANG J, FU W, CHEN C, CHEN W, HUANG W, YANG R, KONG Q, ZHANG B, ZHAO J, CHEN C, LUO J, YANG F, DUAN X, JIANG Z, QIN Y. Atomic design and fine-tuning of subnanometric Pt catalysts to tame hydrogen generation[J]. ACS Catal,2021,11(7):4146−4156. doi: 10.1021/acscatal.0c04614