Synthesis and Property of Platinum-cobalt Alloy Nano Catalyst

doi:10.15541/jim20200253

Abstract

Abstract:

In order to achieve the commercialization of proton exchange membrane fuel cells (PEMFCs), it is necessary to synthesize electrocatalyst with higher electrochemical activity. In this study, PtCo nano-alloy electrocatalyst was prepared by liquid phase synthesis method with sodium borohydride as reducing agent, triethylamine as complexing agent, and by sequential heat-treatment. The physical properties of the catalyst were characterized by different analytical methods. We studied the effects of heat-treatment temperature, different amounts of sodium borohydride and triethylamine on electrochemical performance. The results show that heat-treatment can greatly improve the mass activity of the catalyst, and 500 ℃ is the optimal temperature for preparing the catalyst with the highest catalytic performance towards oxygen reduction reaction(ORR). Compared with commercial TKK-PtCo alloy catalyst under the same test system, the as-prepared catalysts exhibits advantages of more uniform particle size distribution, smaller particle size and higher electrochemical performance. In particular, the mass activity (MA) of the prepared catalyst is 133 mA/mg_Pt, which is 3 times of TKK-PtCo alloy catalyst.

Key words: electrocatalyst, platinum-cobalt alloy, heat-treatment, oxygen reduction reaction, active specific surface area

CLC Number:

O646

ZHU Yong, GU Jun, YU Tao, HE Haitong, YAO Rui. Synthesis and Property of Platinum-cobalt Alloy Nano Catalyst[J]. Journal of Inorganic Materials, 2021, 36(3): 299-305.

Figures/Tables 11

Fig. 1 XRD patterns of Pt2.8Co/C, Pt2.8Co/C-500 and TKK-PtCo/C

Fig. 2 TEM images and particle size distributions of Pt2.8Co/C(a), Pt2.8Co/C-500(b) and TKK-PtCo/C(c)

Fig. 3 EDS mappings of Pt2.8Co/C-500 (a) TEM image; (b) PtCo alloy; (c) Co; (d) Pt

Fig. 4 ECSA histogram for DN-Pt2.8Co/C with different amounts of NaBH4 (a); MA histogram for DTL-Pt2.8Co/C with different amounts of triethylamine (b)

Fig. 5 CV(a) and LSV (b) curves for Pt2.8Co/C, Pt2.8Co/C-500 and TKK-PtCo/C; CV(c, e) and LSV(d, f) curves of Pt2.8Co/C-500 (c, d) and TKK-PtCo/C (e, f) before and after durability tests

Table 1 ECSA and MA parameters of platinum-cobalt alloy nano catalysts

Sample	ECSA/(m²∙g_Pt^-1)	MA/(mA∙mg_Pt^-1)
Pt_2.8Co/C	51.6	54.2
Pt_2.8Co/C-500	43.5	133.0
TKK-PtCo/C	28.1	44.3
ADT-Pt_2.8Co/C-500	24.6	71.0
ADT-TKK-PtCo/C	15.7	27.2

Fig. S1 Energy spectrum of Pt2.8Co/C-500

Fig. S2 CV(a) and LSV(b) curves of TKK-PtCo/C and DN-Pt2.8Co/C

Fig. S3 LSV curves of DTL-Pt2.8Co/C with different triethylamine

Fig. S4 ECSA (a) and MA (b) histograms of Pt2.8Co/C with different heat-treatment temperatures

Fig. S5 TEM images and particle size distribution of ADT-Pt2.8Co/C-500= S

References 28

[1]	毛宗强 . 燃料电池. 化学工业出版社, 2005.
[2]	孙世刚等. 电催化. 北京: 化学工业出版社, 2013: 663.
[3]	SUI S, WANG X, ZHOU X, et al. A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: nanostructure, activity, mechanism and carbon support in PEM fuel cells. J. Mater. Chem. A, 2017,5(5):1808-1825.
[4]	ZHAO L, WANG Q, ZHANG X, et al. Combined electron and structure manipulation on Fe-containing N-doped carbon nanotubes to boost bifunctional oxygen electrocatalysis. ACS Appl. Mater. Int., 2018,10(42):35888-35895.
[5]	GAN J, ZHANG J, ZHANG B, et al. Active sites engineering of Pt/CNT oxygen reduction catalysts by atomic layer deposition. J. Energy Chem., 2020,45:59-66.
[6]	JUNG W S. Study on durability of Pt supported on graphitized carbon under simulated start-up/shut-down conditions for polymer electrolyte membrane fuel cells. J. Energy Chem., 2018,27(1):326-334.
[7]	PENG H, MO Z, LIAO S, et al. High performance Fe- and N- doped carbon catalyst with graphene structure for oxygen reduction. Sci. Rep.-UK, 2013,3(1):1765.
[8]	LUO Y, FENG J Z, FENG J, et al. Research progress on advanced carbon materials as Pt support for proton exchange membrane fuel cells. J. Inorg. Mater., 2020,35(4):407-415.
[9]	LIU J, HE T, WANG Q, et al. Confining ultrasmall bimetal alloys in porous N-carbon as scalable and sustainable electrocatalysts for rechargeable Zn-air batteries. J. Mater. Chem. A, 2019,7:12451.
[10]	LOUISIA S, THOMAS Y R J, LECANTE P, et al. Alloyed Pt₃ M (M=Co, Ni) nanoparticles supported on S- and N-doped carbon nanotubes for the oxygen reduction reaction. Beilstein J. Nanotech., 2019,10(1):1251-1269.
[11]	XU W, LYU F, BAI Y, et al. Porous cobalt oxide nanoplates enriched with oxygen vacancies for oxygen evolution reaction. Nano Energy, 2018,43:110-116.
[12]	CHEN Z, WANG Q, ZHANG X, et al. N-doped defective carbon with trace Co for efficient rechargeable liquid electrolyte-/all-solid-state Zn-air batteries. Science Bulletin, 2018,63(9):548-555.
[13]	BEARD B C. The structure and activity of Pt-Co alloys as oxygen reduction electrocatalysts. J. Electrochem. Soc., 1990,137(11):3368.
[14]	LI S L, YUAN X X, KONG H C, et al. Fe-PPy-TsOH/C as cathode catalyst for proton exchange membrane fuel cells. J. Inorg. Mater., 2017,32(4):393.
[15]	BAI P, TIAN F, WANG H, et al. Electrocatalytic enhancement of 0D/1D/2D multidimensional PtCo alloy@cobalt benzoate/graphene composite catalyst for alcohol electro-oxidation. Advanced Materials Interfaces, 2019,6(19):1900946.
[16]	杨德隆, 顾军, 刘晓梦 , 等. 铂基催化剂氧还原测试技术的研究进展. 电源技术, 2019,43(12):2040-2043.
[17]	WANG G, HILGERT J, RICHTER F H, et al. Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural. Nat. Mater., 2014,13(3):293-300. DOI URL PMID
[18]	ZHANG L, HAN L, LIU H, et al. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media. Angewandte Chemie International Edition, 2017,56(44):13694-13698. DOI URL PMID
[19]	LIN L, ZHOU W, GAO R, et al. Low-temperature hydrogen production from water and methanol using Pt/alpha-MoC catalysts. Nature, 2017,544(7648):80-83. DOI URL PMID
[20]	HUANG H, LI K, CHEN Z, et al. Achieving remarkable activity and durability toward oxygen reduction reaction based on ultrathin Rh-doped Pt nanowires. J. Am. Chem. Soc., 2017,139(24):8152-8159. DOI URL PMID
[21]	STRASSER P, KOH S, ANNIYEV T, et al. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. Nat. Chem., 2010,2(6):454-460. DOI URL PMID
[22]	YANG D, GU J, LIU X, et al. Monodispersed Pt₃Ni nanoparticles as a highly efficient electrocatalyst for PEMFCs. Catalysts, 2019,9(7):588.
[23]	PAQUETTE. Encyclopedia of Reagents for Organic Synthesis. Chichester: Wiley, 1995: 8.
[24]	YAO S, FENG L, ZHAO X, et al. Pt/C catalysts with narrow size distribution prepared by colloidal-precipitation method for methanol electrooxidation. J. Power Sources, 2012,217:280-286.
[25]	ANTOLINI E. Structural parameters of supported fuel cell catalysts: the effect of particle size, inter-particle distance and metal loading on catalytic activity and fuel cell performance. Applied Catalysis B: Environmental, 2016,181:298-313.
[26]	SAHIN N E, NAPPORN T W, DUBAU L, et al. Temperature- dependence of oxygen reduction activity on Pt/C and PtCr/C electrocatalysts synthesized from microwave-heated diethylene glycol method. Applied Catalysis B: Environmental, 2017,203:72-84.
[27]	ARUMUGAM B, TAMAKI T, YAMAGUCHI T. Beneficial role of copper in the enhancement of durability of ordered intermetallic PtFeCu catalyst for electrocatalytic oxygen reduction. ACS Appl. Mater. Int., 2015,7(30):16311-16321.
[28]	KUROKI H, TAMAKI T, MATSUMOTO M, et al. Platinum- iron-nickel trimetallic catalyst with superlattice structure for enhanced oxygen reduction activity and durability. Ind. Eng. Chem. Res., 2016,55(44):11458-11466.