PtRu Particles Supported on Two-dimensional Titanium Carbide/Carbon Nanotubes: Preparation and Electrocatalytic Properties
(2.College of Materials Science and Engineering, Donghua University, Shanghai, China 210050)
【Abstract】Direct methanol fuel cells have good application prospects due to their advantages of convenient operation, high conversion efficiency, low operating temperature, low pollution, and easy storage and transportation of liquid fuel. However, the existing anode catalysts have shortcomings such as low catalytic activity and poor resistance to CO toxicity which restrict their commercial applications. In this study, a series of PtRu/(Ti3C2Tx)0.5-(MWCNTs)0.5 anode catalyst materials with different ratios of Pt to Ru were prepared by three-step method. Ti3C2Tx was obtained by HF corrosion of Ti3AlC2. After the compounding of Ti3C2Tx and acidified multi-walled carbon nanotubes (MWCNTs), Pt and Ru particles were supported by a solvothermal method. The synergistic relationship of Ru and Pt atoms was analyzed by XRD, SEM, EDS, TEM, and XPS. The results showed that the Ru atoms were mixed with the Pt atoms to form PtRu bimetallic alloy with a particle size of about 3.6 nm. The electrochemical results showed that the Pt1Ru0.5/(Ti3C2Tx)0.5-(MWCNTs)0.5 catalyst had the best electrochemical performance. Its electrochemical active area (ECSA) was 139.5 m2/g, and the forward peak current density was 36.4 mA/cm2.
【Keywords】 two-dimensional Ti3C2Tx material; PtRu nanoparticle; direct methanol fuel cells; electrocatalytic performance;
 CHU S, MAJUMDAR A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488 (7411): 294–303.
 WEN Z, LIU J, LI J. Core/shell Pt/C nanoparticles embedded in mesoporous carbon as a methanol-tolerant cathode catalyst in direct methanol fuel cells. Adv. Mater., 2008, 20 (4): 743–747.
 LIU H, SONG C, LEI Z, et al. A review of anode catalysis in the direct methanol fuel cell. J. Power Sources, 2006, 155 (2): 95–110.
 XIAO Z, MIN Y, LIANG M, et al. Recent advances in catalysts for direct methanol fuel cells. Energy Environ. Sci., 2011, 4 (8): 2736–2753.
 LIU M, ZHANG R, CHEN W. Graphene-supported nanoelectrocatalysts for fuel cells: synthesis, properties, and applications.Chem. Rev., 2014, 114 (10): 5117–5160.
 LU S, EID K, GE D, et al. One-pot synthesis of PtRu nanodendrites as efficient catalysts for methanol oxidation reaction. Nanoscale, 2017, 9 (3): 1033–1039.
 LI M, ZHENG H, HAN G, et al. Facile synthesis of binary PtRu nanoflowers for advanced electrocatalysts toward methanol oxidation. Catal. Commun., 2017, 92: 95–99.
 W L J, M S R, E S K, et al. How to make electrocatalysts more active for direct methanol oxidation-avoid PtRu bimetallic alloys! J. Phys. Chem. B, 2000, 104 (42): 9772–9776.
 ZHANG J, CAO H, WANG H. Research progress of novel two-dimensional material MXene. J. Inorg. Mater., 2017, 32 (6): 561–570.
 ZHENG W, SUN Z, ZHANG P, et al. Research progress on MXene, two dimensional nano-materials. Mater. Rev. A, 2017,31 (9): 1–14.
 YU X, YOHAN D A, MICHAEL N, et al. Prediction and characterization of MXene nanosheet anodes for non-lithium-ion batteries. ACS Nano, 2014, 8 (9): 9606–9615.
 WEI Z, LI Y, PEIGEN Z, et al. Energy storage and application for 2D nano-material MXenes. Mater. Rev. A, 2018, 32 (15): 2513–2537.
 YAO S, LI N, YE H, et al. Synthesis of two-dimensional MXene and their applications in electrochemical energy storage. Progress in Chemistry, 2018, 30 (7): 932–946.
 JIANG Y, XIE X, CHEN Y, et al. Hierarchically structured cellulose aerogels with interconnected MXene networks and their enhanced microwave absorption properties. J. Mater. Chem. C, 2018, 6 (32): 8679–8687.
 LIU Y, LUO R, LI Y, et al. Sandwich-like Co3O4/MXene composite with enhanced catalytic performance for bisphenol a degradation. Chem. Eng. J., 2018, 347: 731–740.
 ZHENG H, CHEN J, LI Y. Research on preparation and photocatalytic application of two-dimensional crystal MXene. B. Chin. Ceram. Soc., 2018, 37 (06): 1908–1913.
 MA Y, LIU N, LI L, et al. A highly flexible and sensitive piezoresistive sensor based on MXene with greatly changed interlayer distances. Nat. Commun., 2017, 8 (1): 1207–1215.
 HU Q K, SUN D D, WU Q H, et al. MXene: a new family of promising hydrogen storage medium. J. Phys. Chem. A, 2013, 117 (51): 14253–14260.
 NAGUIB M, MOCHALIN V N, BARSOUM M W, et al. 25th anniversary article: MXenes: a new family of two-dimensional materials. Adv. Mater., 2014, 26 (7): 992–1005.
 XIE X, CHEN S, DING W, et al. An extraordinarily stable catalyst: Pt NPs supported on two-dimensional Ti3C2X2 (X = OH, F) nanosheets for oxygen reduction reaction. Chem. Commun., 2013, 49 (86): 10112–10114.
 WANG G, SUN G, QI W, et al. Effect of carbon black additive in Pt black cathode catalyst layer on direct methanol fuel cell performance. Int. J. Hydrogen Energy, 2010, 35 (20): 11245–11253.
 YAO Z, YUE R, ZHAI C, et al. Electrochemical layer-by-layer fabrication of a novel three-dimensional Pt/graphene/carbon fiber electrode and its improved catalytic performance for methanol electrooxidation in alkaline medium. Int. J. Hydrogen Energy, 2013, 38 (15): 6368–6376.
 KIM H T, YOU D J, YOON H K, et al. Cathode catalyst layer using supported Pt catalyst on ordered mesoporous carbon for direct methanol fuel cell. J. Power Sources, 2014, 180 (2): 724–732.
 LI W, LIANG C, ZHOU W, et al. Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells. J. Phys. Chem. B, 2003, 107 (26): 149–154.
 ZHANG X, ZHU J X, TIWARY C S, et al. Palladium nanoparticles supported on nitrogen and sulfur dual-doped graphene as highly active electrocatalysts for formic acid and methanol oxidation. ACS Appl. Mater. Interfaces, 2016, 8 (17): 10858–10865.
 CHEN W X, ZHAO J, LEE J Y, et al. Microwave heated polyol synthesis of carbon nanotubes supported Pt nanoparticles for methanol electrooxidation. Mater. Chem. Phys., 2005, 91 (1): 124–129.
 WANG Z B, YIN G P, SHI P F. Effects of ozone treatment of carbon support on Pt-Ru/C catalysts performance for direct methanol fuel cell. Carbon, 2006, 44 (1): 133–140.
 ANTONUCCI P L, ALDERUCCI V, GIORDANO N, et al. On the role of surface functional groups in Pt carbon interaction. J. Appl. Electrochem., 1994, 24 (1): 58–65.
 WILHELMSSON O, PALMQUIST J P, LEWIN E, et al. Deposition and characterization of ternary thin films within the Ti-Al-C system by DC magnetron sputtering. J. Cryst. Growth, 2006, 291 (1): 290–300.
 QIU J D, WANG G C, LIANG R P, et al. Controllable deposition of platinum nanoparticles on graphene as an electrocatalyst for direct methanol fuel cells. J. Phys. Chem. C, 2011, 115 (31): 15639–15645.
 ZHANG Y, CHANG G, SHU H, et al. Synthesis of Pt-Pd bimetallic nanoparticles anchored on graphene for highly active methanol electro-oxidation. J. Power Sources, 2014, 262 (262): 279–285.
 YANG X, YANG Q, XU J, et al. Bimetallic PtPd nanoparticles on Nafion-graphene film as catalyst for ethanol electro-oxidation. J. Mater. Chem., 2012, 22 (16): 8057–8062.
 HUANG H, ZHU J, ZHANG W, et al. Controllable codoping of nitrogen and sulfur in graphene for highly efficient Li-oxygen batteries and direct methanol fuel cells. Chem. Mater., 2016, 28 (6): 1737–1745.
 ZHANG X, ZHANG J, HUANG H, et al. Platinum nanoparticles anchored on graphene oxide-dispersed pristine carbon nanotube supports: high-performance electrocatalysts toward methanol electrooxidation. Electrochim. Acta, 2017, 258: 919–926.
 SU F, TIAN Z, POH C K, et al. Pt nanoparticles supported on nitrogen-doped porous carbon nanospheres as an electrocatalyst for fuel cells. Chem. Mater., 2010, 22 (3): 832–839.
 ZHANG B, PAN Z C, YU K, et al. Titanium vanadium nitride supported Pt nanoparticles as high-performance catalysts for methanol oxidation reaction. J. Solid State Electrochem., 2017, 21 (10): 3065–3070.
 HUANG H, ZHU J, LI D, et al. Pt nanoparticles grown on 3D RuO2-modified graphene architectures for highly efficient methanol oxidation. J. Mater. Chem. A, 2017, 5 (9): 4560–4567.
 GAO Z, LI M, WANG J, et al. Pt nanocrystals grown on three-dimensional architectures made from graphene and MoS2 nanosheets: highly efficient multifunctional electrocatalysts toward hydrogen evolution and methanol oxidation reactions. Carbon, 2018, 139: 369–377.