ISSN 0253-2778

CN 34-1054/N

Open AccessOpen Access JUSTC Chemistry 05 June 2023

Mercaptopropane-assisted synthesis of graphitic carbon-supported Pt nanoparticles for enhancing fuel cell start-stop performance

Cite this:
https://doi.org/10.52396/JUSTC-2023-0051
More Information
  • Author Bio:

    Qian-Qian Yang is presently a graduate student at the University of Science and Technology of China. Her research interests focus on the carbon support durability of fuel cell Pt cathode catalysts and the fabrication of small-sized Pt nanoparticles on graphitic carbons

    Lei Tong received his Ph.D. degree from the University of Science and Technology of China (USTC) in 2020 under the supervision of Prof. Hai-Wei Liang. Currently, he is a postdoctoral researcher at USTC working with Prof. Hai-Wei Liang. His research mainly focuses on the fabrication and application of Pt-based cathode catalysts for fuel cell applications

    Hai-Wei Liang received his Ph.D. degree under the supervision of Prof. Shu-Hong Yu at the University of Science and Technology of China (USTC) in 2011. Following this, he spent three and a half years as a postdoctoral fellow at the Max Planck Institute of Polymer Research (Germany), working alongside Prof. Klaus Müllen and Prof. Xinliang Feng. In 2016, he returned to USTC as a Full Professor. His research focuses on engineering the thermal decomposition chemistry of small molecules to synthesize functional carbon materials, as well as developing high-performance carbon-supported Pt and Pt alloy catalysts for fuel cell applications

  • Corresponding author: E-mail: ltong17@mail.ustc.edu.cn; E-mail: hwliang@ustc.edu.cn
  • Received Date: 24 March 2023
  • Accepted Date: 26 April 2023
  • Available Online: 05 June 2023
  • Although graphitic carbons, as a support for the cathode catalyst in proton exchange membrane fuel cells, have significant advantages in enhancing the corrosion resistance of the catalyst, the preparation of small-sized Pt particles on the graphitic carbon support often faces challenges due to its low porosity and lack of defect structures. Here, we report a mercaptopropane-assisted impregnation method to achieve size control of Pt nanoparticles on graphitic carbon. We show that mercaptopropane can coordinate with Pt during the impregnation process and transform into sulfur-doped carbon coatings through the subsequent thermal reduction process, which ensures the formation of small-sized Pt nanoparticles on graphitic carbon. Due to effective size control, the prepared cathode catalyst exhibited enhanced fuel cell performance compared to the catalyst prepared by the traditional impregnation method. We performed the accelerated stress test on the synthesized catalyst using the durability protocol recommended by the U.S. Department of Energy (DOE). After 5000 voltage cycles in the range of 1.0–1.5 V, the catalyst showed a negligible voltage loss of only 10 mV at a current density of 1.5 A·cm−2, meeting the DOE support durability target (30 mV).
    Mercaptopropane-assisted synthesis of graphitic carbon supported small-sized Pt nanoparticles.
    Although graphitic carbons, as a support for the cathode catalyst in proton exchange membrane fuel cells, have significant advantages in enhancing the corrosion resistance of the catalyst, the preparation of small-sized Pt particles on the graphitic carbon support often faces challenges due to its low porosity and lack of defect structures. Here, we report a mercaptopropane-assisted impregnation method to achieve size control of Pt nanoparticles on graphitic carbon. We show that mercaptopropane can coordinate with Pt during the impregnation process and transform into sulfur-doped carbon coatings through the subsequent thermal reduction process, which ensures the formation of small-sized Pt nanoparticles on graphitic carbon. Due to effective size control, the prepared cathode catalyst exhibited enhanced fuel cell performance compared to the catalyst prepared by the traditional impregnation method. We performed the accelerated stress test on the synthesized catalyst using the durability protocol recommended by the U.S. Department of Energy (DOE). After 5000 voltage cycles in the range of 1.0–1.5 V, the catalyst showed a negligible voltage loss of only 10 mV at a current density of 1.5 A·cm−2, meeting the DOE support durability target (30 mV).
    • A scalable and simple mercaptopropane-assisted impregnation method was developed for the preparation of small Pt nanoparticles on graphitic carbons.
    • The resulting graphitic carbon-supported Pt nanoparticle catalysts demonstrated high durability under start-stop fuel cell operation.

  • loading
  • [1]
    Gröger O, Gasteiger H A, Suchsland J P. Erratum: Review—Electromobility: Batteries or fuel cells? [J. Electrochem. Soc., 162, A2605 (2015)]. J. Electrochem. Soc., 2016, 163 (7): X3. doi: 10.1149/2.0431607jes
    [2]
    Gasteiger H A, Panels J E, Yan S G. Dependence of PEM fuel cell performance on catalyst loading. J. Power Sources, 2004, 127 (1/2): 162–171. doi: 10.1016/j.jpowsour.2003.09.013
    [3]
    Harzer G S, Schwämmlein J N, Damjanović A M, et al. Cathode loading impact on voltage cycling induced PEMFC degradation: A voltage loss analysis. J. Electrochem. Soc., 2018, 165 (6): F3118–F3131. doi: 10.1149/2.0161806jes
    [4]
    Nesselberger M, Ashton S, Meier J C, et al. The particle size effect on the oxygen reduction reaction activity of Pt catalysts: Influence of electrolyte and relation to single crystal models. J. Am. Chem. Soc., 2011, 133 (43): 17428–17433. doi: 10.1021/ja207016u
    [5]
    Stamenkovic V, Markovic N M. Tailored high performance low-PGM alloy cathode catalysts. In: 2018 DOE Hydrogen and Fuel Cells Program Review. The U.S. Department of Energy, 2018.
    [6]
    Sattler M L, Ross P N. The surface structure of Pt crystallites supported on carbon black. Ultramicroscopy, 1986, 20 (1/2): 21–28. doi: 10.1016/0304-3991(86)90163-4
    [7]
    Mayrhofer K J J, Blizanac B B, Arenz M, et al. The impact of geometric and surface electronic properties of Pt-catalysts on the particle size effect in electrocatalysis. J. Phys. Chem. B, 2005, 109 (30): 14433–14440. doi: 10.1021/jp051735z
    [8]
    Perez-Alonso F J, McCarthy D N, Nierhoff A, et al. The effect of size on the oxygen electroreduction activity of mass-selected platinum nanoparticles. Angew. Chem. Int. Ed., 2012, 51 (19): 4641–4643. doi: 10.1002/anie.201200586
    [9]
    Sheng W, Chen S, Vescovo E, et al. Size influence on the oxygen reduction reaction activity and instability of supported Pt nanoparticles. J. Electrochem. Soc., 2011, 159 (2): B96–B103. doi: 10.1149/2.009202jes
    [10]
    Meier J C, Galeano C, Katsounaros I, et al. Design criteria for stable Pt/C fuel cell catalysts. Beilstein J. Nanotechnol., 2014, 5 (1): 44–67. doi: 10.3762/bjnano.5.5
    [11]
    Yin P, Hu S, Qian K, et al. Quantification of critical particle distance for mitigating catalyst sintering. Nat. Commun., 2021, 12 (1): 4865. doi: 10.1038/s41467-021-25116-2
    [12]
    Padgett E, Yarlagadda V, Holtz M E, et al. Mitigation of PEM fuel cell catalyst degradation with porous carbon supports. J. Electrochem. Soc., 2019, 166 (4): F198–F207. doi: 10.1149/2.0371904jes
    [13]
    Reiser C A, Bregoli L, Patterson T W, et al. A reverse-current decay mechanism for fuel cells. Electrochem. Solid-State Lett., 2005, 8 (6): A273. doi: 10.1149/1.1896466
    [14]
    Mittermeier T, Weiß A, Hasché F, et al. PEM fuel cell start-up/shut-down losses vs temperature for non-graphitized and graphitized cathode carbon supports. J. Electrochem. Soc., 2017, 164 (2): F127–F137. doi: 10.1149/2.1061702jes
    [15]
    Tang H, Qi Z, Ramani M, et al. PEM fuel cell cathode carbon corrosion due to the formation of air/fuel boundary at the anode. J. Power Sources, 2006, 158 (2): 1306–1312. doi: 10.1016/j.jpowsour.2005.10.059
    [16]
    Devilliers D, Mahé É. Cellules électrochimiques: aspects thermodynamiques et cinétiques. L’Actualité Chimique, 2003, 1: 31–40.
    [17]
    Yamashita Y, Itami S, Takano J, et al. Durability of Pt catalysts supported on graphitized carbon-black during gas-exchange start-up operation similar to that used for fuel cell vehicles. J. Electrochem. Soc., 2016, 163 (7): F644–F650. doi: 10.1149/2.0771607jes
    [18]
    Kneer A, Jankovic J, Susac D, et al. Correlation of changes in electrochemical and structural parameters due to voltage cycling induced degradation in PEM fuel cells. J. Electrochem. Soc., 2018, 165 (6): F3241–F3250. doi: 10.1149/2.0271806jes
    [19]
    Macauley N, Papadias D D, Fairweather J, et al. Carbon corrosion in PEM fuel cells and the development of accelerated stress tests. J. Electrochem. Soc., 2018, 165 (6): F3148–F3160. doi: 10.1149/2.0061806jes
    [20]
    Takahashi T, Ikeda T, Murata K, et al. Accelerated durability testing of fuel cell stacks for commercial automotive applications: A case study. J. Electrochem. Soc., 2022, 169 (4): 044523. doi: 10.1149/1945-7111/ac662d
    [21]
    Borup R L, Kusoglu A, Neyerlin K C, et al. Recent developments in catalyst-related PEM fuel cell durability. Curr. Opin. Electroche., 2020, 21: 192–200. doi: 10.1016/j.coelec.2020.02.007
    [22]
    Yu Y, Li H, Wang H, et al. A review on performance degradation of proton exchange membrane fuel cells during startup and shutdown processes: Causes, consequences, and mitigation strategies. J. Power Sources, 2012, 205: 10–23. doi: 10.1016/j.jpowsour.2012.01.059
    [23]
    Linse N, Scherer G G, Wokaun A, et al. Quantitative analysis of carbon corrosion during fuel cell start-up and shut-down by anode purging. J. Power Sources, 2012, 219: 240–248. doi: 10.1016/j.jpowsour.2012.07.037
    [24]
    Wang G J, Yu Y, Liu H, et al. Progress on design and development of polymer electrolyte membrane fuel cell systems for vehicle applications: A review. Fuel Process. Technol., 2018, 179: 203–228. doi: 10.1016/j.fuproc.2018.06.013
    [25]
    Zhang T, Wang P Q, Chen H C, et al. A review of automotive proton exchange membrane fuel cell degradation under start-stop operating condition. Appl. Energ., 2018, 223: 249–262. doi: 10.1016/j.apenergy.2018.04.049
    [26]
    Higgins D, Hoque M A, Seo M H, et al. Development and simulation of sulfur-doped graphene supported platinum with exemplary stability and activity towards oxygen reduction. Adv. Funct. Mater., 2014, 24 (27): 4325–4336. doi: 10.1002/adfm.201400161
    [27]
    Parrondo J, Han T, Niangar E, et al. Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles. Proc. Natl. Acad. Sci. U. S. A., 2014, 111 (1): 45–50. doi: 10.1073/pnas.1319663111
    [28]
    Huang S Y, Ganesan P, Park S, et al. Development of a titanium dioxide-supported platinum catalyst with ultrahigh stability for polymer electrolyte membrane fuel cell applications. J. Am. Chem. Soc., 2009, 131 (39): 13898–13899. doi: 10.1021/ja904810h
    [29]
    Zhang W, Cao Z, Zhang J, et al. Enhanced durability of Pt-based electrocatalysts in high-temperature polymer electrolyte membrane fuel cells using a graphitic carbon nitride nanosheet support. ACS Sustainable Chem. Eng., 2020, 8 (24): 9195–9205. doi: 10.1021/acssuschemeng.0c03238
    [30]
    Wang L, Yue S, Zhang Q, et al. Morphological and chemical tuning of high-energy-density metal oxides for lithium ion battery electrode applications. ACS Energy Lett., 2017, 2 (6): 1465–1478. doi: 10.1021/acsenergylett.7b00222
    [31]
    Xiong W, Yin H, Wu T, et al. Challenges and opportunities of transition metal oxides as electrocatalysts. Chem. Eur. J., 2023, 29 (5): e202202872. doi: 10.1002/chem.202202872
    [32]
    Qiao Z, Hwang S, Li X, et al. 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: A balance between graphitization and hierarchical porosity. Energy Environ. Sci., 2019, 12 (9): 2830–2841. doi: 10.1039/C9EE01899A
    [33]
    Yano H, Akiyama T, Bele P, et al. Durability of Pt/graphitized carboncatalysts for the oxygenreduction reaction prepared by the nanocapsule method. Phys. Chem. Chem. Phys., 2010, 12 (15): 3806–3814. doi: 10.1039/b923460h
    [34]
    Lee M, Uchida M, Okaya K, et al. Durability of Pt/graphitized carbon catalyst prepared by the nanocapsule method for the start/stop operating condition of polymer electrolyte fuel cells. Electrochemistry, 2011, 79 (5): 381–387. doi: 10.5796/electrochemistry.79.381
    [35]
    Song T W, Xu C, Sheng Z T, et al. Small molecule-assisted synthesis of carbon supported platinum intermetallic fuel cell catalysts. Nat. Commun., 2022, 13 (1): 6521. doi: 10.1038/s41467-022-34037-7
    [36]
    Kabir S, Myers D J, Kariuki N, et al. Elucidating the dynamic nature of fuel cell electrodes as a function of conditioning: An ex situ material characterization and in situ electrochemical diagnostic study. ACS Appl. Mater. Inter., 2019, 11 (48): 45016–45030. doi: 10.1021/acsami.9b11365
    [37]
    Andrews R, Jacques D, Qian D, et al. Purification and structural annealing of multiwalled carbon nanotubes at graphitization temperatures. Carbon, 2001, 39 (11): 1681–1687. doi: 10.1016/S0008-6223(00)00301-8
    [38]
    Endo M, Nishimura K, Kim Y A, et al. Raman spectroscopic characterization of submicron vapor-grown carbon fibers and carbon nanofibers obtained by pyrolyzing hydrocarbons. J. Mater. Res., 1999, 14 (12): 4474–4477. doi: 10.1557/JMR.1999.0607
    [39]
    Shelimov B, Lambert J F, Che M, et al. Initial steps of the alumina-supported platinum catalyst preparation: A molecular study by 195Pt NMR, UV–visible, EXAFS, and Raman spectroscopy. J. Catal., 1999, 185 (2): 462–478. doi: 10.1006/jcat.1999.2527
    [40]
    Jin Z S, Chen Z S, Li Q L, et al. On the conditions and mechanism of PtO2 formation in the photoinduced conversion of H2PtCl6. J. Photoch. Photobio. A, 1994, 81: 177–182. doi: 10.1016/1010-6030(94)03792-2
    [41]
    Gomez S, Erades L, Philippot K, et al. Platinum colloids stabilized by bifunctional ligands: self-organization and connection to gold. Chem. Commun., 2001: 1474–1475. doi: 10.1039/B103781C
    [42]
    Hidai S, Kobayashi M, Niwa H, et al. Platinum oxidation responsible for degradation of platinum-cobalt alloy cathode catalysts for polymer electrolyte fuel cells. J. Power Sources, 2012, 215: 233–239. doi: 10.1016/j.jpowsour.2012.05.001
    [43]
    Yang C L, Wang L N, Yin P, et al. Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science, 2021, 374 (6566): 459–464. doi: 10.1126/science.abj9980
  • 加载中

Catalog

    Figure  1.  (a–c) XRD patterns, (d) Raman spectra, (e) nitrogen adsorption-desorption isotherms, and (f) specific surface areas and pore volumes of KJ600, KJ600-2500, and KJ600-3000.

    Figure  2.  (a–c) XRD patterns, (d–f) high-resolution TEM images, and (g–i) particle size distributions of Pt-S/KJ600-2500, Pt-S/KJ600-3000, and Pt/KJ600-3000. The particle size distributions were determined by the statistical results from high-resolution TEM images.

    Figure  3.  (a) UV‒vis spectra of the H2PtCl6·6H2O and H2PtCl6·6H2O/mercaptopropane solutions. (b) XPS results of the Pt 4f orbital of the mercaptopropane-Pt/C and Pt/C precursor powders. (c) R space of the XAFS results of the standard Pt foil, PtS2, and Pt catalysts prepared with and without mercaptopropane. (d) High-resolution TEM images of Pt-S/KJ600-3000. (e) HAADF-STEM and EDS mapping images of Pt-S/KJ600-3000.

    Figure  4.  (a) H2-air polarization curves of Pt-S/KJ600-2500, Pt-S/KJ600-3000 and Pt/KJ600-3000. (b, c) Durability of Pt-S/KJ600-2500 (b) and Pt-S/KJ600-3000 (c) after 5000 voltage cycles in the range of 1.0–1.5 V. (d) ECSA changes of Pt-S/KJ600-2500 and Pt-S/KJ600-3000 before and after 5000 voltage cycles in the range of 1.0–1.5 V. (e, f) SEM images of Pt-S/KJ600-3000 (e) before and (f) after 5000 voltage cycles in the range of 1.0–1.5 V.

    [1]
    Gröger O, Gasteiger H A, Suchsland J P. Erratum: Review—Electromobility: Batteries or fuel cells? [J. Electrochem. Soc., 162, A2605 (2015)]. J. Electrochem. Soc., 2016, 163 (7): X3. doi: 10.1149/2.0431607jes
    [2]
    Gasteiger H A, Panels J E, Yan S G. Dependence of PEM fuel cell performance on catalyst loading. J. Power Sources, 2004, 127 (1/2): 162–171. doi: 10.1016/j.jpowsour.2003.09.013
    [3]
    Harzer G S, Schwämmlein J N, Damjanović A M, et al. Cathode loading impact on voltage cycling induced PEMFC degradation: A voltage loss analysis. J. Electrochem. Soc., 2018, 165 (6): F3118–F3131. doi: 10.1149/2.0161806jes
    [4]
    Nesselberger M, Ashton S, Meier J C, et al. The particle size effect on the oxygen reduction reaction activity of Pt catalysts: Influence of electrolyte and relation to single crystal models. J. Am. Chem. Soc., 2011, 133 (43): 17428–17433. doi: 10.1021/ja207016u
    [5]
    Stamenkovic V, Markovic N M. Tailored high performance low-PGM alloy cathode catalysts. In: 2018 DOE Hydrogen and Fuel Cells Program Review. The U.S. Department of Energy, 2018.
    [6]
    Sattler M L, Ross P N. The surface structure of Pt crystallites supported on carbon black. Ultramicroscopy, 1986, 20 (1/2): 21–28. doi: 10.1016/0304-3991(86)90163-4
    [7]
    Mayrhofer K J J, Blizanac B B, Arenz M, et al. The impact of geometric and surface electronic properties of Pt-catalysts on the particle size effect in electrocatalysis. J. Phys. Chem. B, 2005, 109 (30): 14433–14440. doi: 10.1021/jp051735z
    [8]
    Perez-Alonso F J, McCarthy D N, Nierhoff A, et al. The effect of size on the oxygen electroreduction activity of mass-selected platinum nanoparticles. Angew. Chem. Int. Ed., 2012, 51 (19): 4641–4643. doi: 10.1002/anie.201200586
    [9]
    Sheng W, Chen S, Vescovo E, et al. Size influence on the oxygen reduction reaction activity and instability of supported Pt nanoparticles. J. Electrochem. Soc., 2011, 159 (2): B96–B103. doi: 10.1149/2.009202jes
    [10]
    Meier J C, Galeano C, Katsounaros I, et al. Design criteria for stable Pt/C fuel cell catalysts. Beilstein J. Nanotechnol., 2014, 5 (1): 44–67. doi: 10.3762/bjnano.5.5
    [11]
    Yin P, Hu S, Qian K, et al. Quantification of critical particle distance for mitigating catalyst sintering. Nat. Commun., 2021, 12 (1): 4865. doi: 10.1038/s41467-021-25116-2
    [12]
    Padgett E, Yarlagadda V, Holtz M E, et al. Mitigation of PEM fuel cell catalyst degradation with porous carbon supports. J. Electrochem. Soc., 2019, 166 (4): F198–F207. doi: 10.1149/2.0371904jes
    [13]
    Reiser C A, Bregoli L, Patterson T W, et al. A reverse-current decay mechanism for fuel cells. Electrochem. Solid-State Lett., 2005, 8 (6): A273. doi: 10.1149/1.1896466
    [14]
    Mittermeier T, Weiß A, Hasché F, et al. PEM fuel cell start-up/shut-down losses vs temperature for non-graphitized and graphitized cathode carbon supports. J. Electrochem. Soc., 2017, 164 (2): F127–F137. doi: 10.1149/2.1061702jes
    [15]
    Tang H, Qi Z, Ramani M, et al. PEM fuel cell cathode carbon corrosion due to the formation of air/fuel boundary at the anode. J. Power Sources, 2006, 158 (2): 1306–1312. doi: 10.1016/j.jpowsour.2005.10.059
    [16]
    Devilliers D, Mahé É. Cellules électrochimiques: aspects thermodynamiques et cinétiques. L’Actualité Chimique, 2003, 1: 31–40.
    [17]
    Yamashita Y, Itami S, Takano J, et al. Durability of Pt catalysts supported on graphitized carbon-black during gas-exchange start-up operation similar to that used for fuel cell vehicles. J. Electrochem. Soc., 2016, 163 (7): F644–F650. doi: 10.1149/2.0771607jes
    [18]
    Kneer A, Jankovic J, Susac D, et al. Correlation of changes in electrochemical and structural parameters due to voltage cycling induced degradation in PEM fuel cells. J. Electrochem. Soc., 2018, 165 (6): F3241–F3250. doi: 10.1149/2.0271806jes
    [19]
    Macauley N, Papadias D D, Fairweather J, et al. Carbon corrosion in PEM fuel cells and the development of accelerated stress tests. J. Electrochem. Soc., 2018, 165 (6): F3148–F3160. doi: 10.1149/2.0061806jes
    [20]
    Takahashi T, Ikeda T, Murata K, et al. Accelerated durability testing of fuel cell stacks for commercial automotive applications: A case study. J. Electrochem. Soc., 2022, 169 (4): 044523. doi: 10.1149/1945-7111/ac662d
    [21]
    Borup R L, Kusoglu A, Neyerlin K C, et al. Recent developments in catalyst-related PEM fuel cell durability. Curr. Opin. Electroche., 2020, 21: 192–200. doi: 10.1016/j.coelec.2020.02.007
    [22]
    Yu Y, Li H, Wang H, et al. A review on performance degradation of proton exchange membrane fuel cells during startup and shutdown processes: Causes, consequences, and mitigation strategies. J. Power Sources, 2012, 205: 10–23. doi: 10.1016/j.jpowsour.2012.01.059
    [23]
    Linse N, Scherer G G, Wokaun A, et al. Quantitative analysis of carbon corrosion during fuel cell start-up and shut-down by anode purging. J. Power Sources, 2012, 219: 240–248. doi: 10.1016/j.jpowsour.2012.07.037
    [24]
    Wang G J, Yu Y, Liu H, et al. Progress on design and development of polymer electrolyte membrane fuel cell systems for vehicle applications: A review. Fuel Process. Technol., 2018, 179: 203–228. doi: 10.1016/j.fuproc.2018.06.013
    [25]
    Zhang T, Wang P Q, Chen H C, et al. A review of automotive proton exchange membrane fuel cell degradation under start-stop operating condition. Appl. Energ., 2018, 223: 249–262. doi: 10.1016/j.apenergy.2018.04.049
    [26]
    Higgins D, Hoque M A, Seo M H, et al. Development and simulation of sulfur-doped graphene supported platinum with exemplary stability and activity towards oxygen reduction. Adv. Funct. Mater., 2014, 24 (27): 4325–4336. doi: 10.1002/adfm.201400161
    [27]
    Parrondo J, Han T, Niangar E, et al. Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles. Proc. Natl. Acad. Sci. U. S. A., 2014, 111 (1): 45–50. doi: 10.1073/pnas.1319663111
    [28]
    Huang S Y, Ganesan P, Park S, et al. Development of a titanium dioxide-supported platinum catalyst with ultrahigh stability for polymer electrolyte membrane fuel cell applications. J. Am. Chem. Soc., 2009, 131 (39): 13898–13899. doi: 10.1021/ja904810h
    [29]
    Zhang W, Cao Z, Zhang J, et al. Enhanced durability of Pt-based electrocatalysts in high-temperature polymer electrolyte membrane fuel cells using a graphitic carbon nitride nanosheet support. ACS Sustainable Chem. Eng., 2020, 8 (24): 9195–9205. doi: 10.1021/acssuschemeng.0c03238
    [30]
    Wang L, Yue S, Zhang Q, et al. Morphological and chemical tuning of high-energy-density metal oxides for lithium ion battery electrode applications. ACS Energy Lett., 2017, 2 (6): 1465–1478. doi: 10.1021/acsenergylett.7b00222
    [31]
    Xiong W, Yin H, Wu T, et al. Challenges and opportunities of transition metal oxides as electrocatalysts. Chem. Eur. J., 2023, 29 (5): e202202872. doi: 10.1002/chem.202202872
    [32]
    Qiao Z, Hwang S, Li X, et al. 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: A balance between graphitization and hierarchical porosity. Energy Environ. Sci., 2019, 12 (9): 2830–2841. doi: 10.1039/C9EE01899A
    [33]
    Yano H, Akiyama T, Bele P, et al. Durability of Pt/graphitized carboncatalysts for the oxygenreduction reaction prepared by the nanocapsule method. Phys. Chem. Chem. Phys., 2010, 12 (15): 3806–3814. doi: 10.1039/b923460h
    [34]
    Lee M, Uchida M, Okaya K, et al. Durability of Pt/graphitized carbon catalyst prepared by the nanocapsule method for the start/stop operating condition of polymer electrolyte fuel cells. Electrochemistry, 2011, 79 (5): 381–387. doi: 10.5796/electrochemistry.79.381
    [35]
    Song T W, Xu C, Sheng Z T, et al. Small molecule-assisted synthesis of carbon supported platinum intermetallic fuel cell catalysts. Nat. Commun., 2022, 13 (1): 6521. doi: 10.1038/s41467-022-34037-7
    [36]
    Kabir S, Myers D J, Kariuki N, et al. Elucidating the dynamic nature of fuel cell electrodes as a function of conditioning: An ex situ material characterization and in situ electrochemical diagnostic study. ACS Appl. Mater. Inter., 2019, 11 (48): 45016–45030. doi: 10.1021/acsami.9b11365
    [37]
    Andrews R, Jacques D, Qian D, et al. Purification and structural annealing of multiwalled carbon nanotubes at graphitization temperatures. Carbon, 2001, 39 (11): 1681–1687. doi: 10.1016/S0008-6223(00)00301-8
    [38]
    Endo M, Nishimura K, Kim Y A, et al. Raman spectroscopic characterization of submicron vapor-grown carbon fibers and carbon nanofibers obtained by pyrolyzing hydrocarbons. J. Mater. Res., 1999, 14 (12): 4474–4477. doi: 10.1557/JMR.1999.0607
    [39]
    Shelimov B, Lambert J F, Che M, et al. Initial steps of the alumina-supported platinum catalyst preparation: A molecular study by 195Pt NMR, UV–visible, EXAFS, and Raman spectroscopy. J. Catal., 1999, 185 (2): 462–478. doi: 10.1006/jcat.1999.2527
    [40]
    Jin Z S, Chen Z S, Li Q L, et al. On the conditions and mechanism of PtO2 formation in the photoinduced conversion of H2PtCl6. J. Photoch. Photobio. A, 1994, 81: 177–182. doi: 10.1016/1010-6030(94)03792-2
    [41]
    Gomez S, Erades L, Philippot K, et al. Platinum colloids stabilized by bifunctional ligands: self-organization and connection to gold. Chem. Commun., 2001: 1474–1475. doi: 10.1039/B103781C
    [42]
    Hidai S, Kobayashi M, Niwa H, et al. Platinum oxidation responsible for degradation of platinum-cobalt alloy cathode catalysts for polymer electrolyte fuel cells. J. Power Sources, 2012, 215: 233–239. doi: 10.1016/j.jpowsour.2012.05.001
    [43]
    Yang C L, Wang L N, Yin P, et al. Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science, 2021, 374 (6566): 459–464. doi: 10.1126/science.abj9980

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