Platinum nanoparticle decorated vertically aligned graphene screen-printed electrodes: electrochemical characterisation and exploration towards the hydrogen evolution reaction.

We present the fabrication of platinum (Pt0) nanoparticle (ca. 3 nm average diameter) decorated vertically aligned graphene (VG) screen-printed electrodes (Pt/VG-SPE) and explore their physicochemical characteristics and electrocatalytic activity towards the hydrogen evolution reaction (HER) in acidic media (0.5 M H2SO4). The Pt/VG-SPEs exhibit remarkable HER activity with an overpotential (recorded at -10 mA cm-2) and Tafel value of 47 mV (vs. RHE) and 27 mV dec-1. These values demonstrate the Pt/VG-SPEs as significantly more electrocatalytic than a bare/unmodified VG-SPE (789 mV (vs. RHE) and 97 mV dec-1). The uniform coverage of Pt0 nanoparticles (ca. 3 nm) upon the VG-SPE support results in a low loading of Pt0 nanoparticles (ca. 4 μg cm-2), yet yields comparable HER activity to optimal Pt based catalysts reported in the literature, with the advantages of being comparatively cheap, highly reproducible and tailorable platforms for HER catalysis. In order to test any potential dissolution of Pt0 from the Pt/VG-SPE surface, which is a key consideration for any HER catalyst, we additively manufactured (AM) a bespoke electrochemical flow cell that allowed for the electrolyte to be collected at regular intervals and analysed via inductively coupled plasma optical emission spectroscopy (ICP-OES). The AM electrochemical cell can be rapidly tailored to a plethora of geometries making it compatible with any size/shape of electrochemical platform. This work presents a novel and highly competitive HER platform and a novel AM technique for exploring the extent of Pt0 nanoparticle dissolution upon the electrode surface, making it an essential study for those seeking to test the stability/catalyst discharge of their given electrochemical platforms.

[1]  R. Borup,et al.  Recent developments in catalyst-related PEM fuel cell durability , 2020, Current Opinion in Electrochemistry.

[2]  Luhua Jiang,et al.  PANI-modified Pt/Na4Ge9O20 with low Pt loadings: Efficient bifunctional electrocatalyst for oxygen reduction and hydrogen evolution , 2019, International Journal of Hydrogen Energy.

[3]  D. A. Brownson,et al.  Investigating the Integrity of Graphene towards the Electrochemical Hydrogen Evolution Reaction (HER) , 2019, Scientific Reports.

[4]  Omar J. Guerra,et al.  Cost Competitiveness of Electrolytic Hydrogen , 2019, Joule.

[5]  Y. Sung,et al.  A highly durable carbon-nanofiber-supported Pt–C core–shell cathode catalyst for ultra-low Pt loading proton exchange membrane fuel cells: facile carbon encapsulation , 2019, Energy & Environmental Science.

[6]  K. Mouralova,et al.  Study of vertical graphene growth on silver substrate based on design of experiment , 2019, Diamond and Related Materials.

[7]  Jinhua Chen,et al.  Low-cost high-performance hydrogen evolution electrocatalysts based on Pt-CoP polyhedra with low Pt loading in both alkaline and neutral media. , 2019, Dalton transactions.

[8]  Kang Jiang,et al.  Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction , 2019, Nature Communications.

[9]  C. Ekberg,et al.  An Efficient Leaching of Palladium from Spent Catalysts through Oxidation with Fe(III) , 2019, Materials.

[10]  Zhongfan Liu,et al.  Transparent Electrothermal Heaters Based on Vertically-Oriented Graphene Glass Hybrid Materials , 2019, Nanomaterials.

[11]  Zhichuan J. Xu,et al.  Recommended Practices and Benchmark Activity for Hydrogen and Oxygen Electrocatalysis in Water Splitting and Fuel Cells , 2019, Advanced materials.

[12]  Xien Liu,et al.  Pt-C Interfaces Based on Electronegativity-Functionalized Hollow Carbon Spheres for Highly Efficient Hydrogen Evolution. , 2018, ACS applied materials & interfaces.

[13]  R. Haas,et al.  Economic prospects and policy framework for hydrogen as fuel in the transport sector , 2018, Energy Policy.

[14]  Syed Mubeen,et al.  Low-Loading of Pt Nanoparticles on 3D Carbon Foam Support for Highly Active and Stable Hydrogen Production , 2018, Front. Chem..

[15]  Lei Yang,et al.  Simultaneous formation of carbon nanosheet and loading of platinum nanoparticle to form platinum/carbon nanosheet composite and its electrocatalytic activity , 2018, Diamond and Related Materials.

[16]  Hanqing Zhao,et al.  Fluorine-doped graphene with an outstanding electrocatalytic performance for efficient oxygen reduction reaction in alkaline solution , 2018, Royal Society Open Science.

[17]  Hong Zhao,et al.  Synthesis of phosphorus-iridium nanocrystals and their superior electrocatalytic activity for oxygen evolution reaction , 2018, Electrochemistry Communications.

[18]  M. Mehrpooya,et al.  A comprehensive review on coupling different types of electrolyzer to renewable energy sources , 2018, Energy.

[19]  C. Banks,et al.  Magnetron Sputter-Coated Nanoparticle MoS2 Supported on Nanocarbon: A Highly Efficient Electrocatalyst toward the Hydrogen Evolution Reaction , 2018, ACS omega.

[20]  Huaiguo Xue,et al.  A FeP powder electrocatalyst for the hydrogen evolution reaction , 2018, Electrochemistry Communications.

[21]  Christopher W. Foster,et al.  Determination of the Electrochemical Area of Screen-Printed Electrochemical Sensing Platforms , 2018, Biosensors.

[22]  Changpeng Liu,et al.  Enhanced electrocatalytic performance for the hydrogen evolution reaction through surface enrichment of platinum nanoclusters alloying with ruthenium in situ embedded in carbon , 2018 .

[23]  Yan Yu,et al.  Exploring hydrogen molybdenum bronze for sodium ion storage: Performance enhancement by vertical graphene core and conductive polymer shell , 2018 .

[24]  C. Guan,et al.  Pt decorated 3D vertical graphene nanosheet arrays for efficient methanol oxidation and hydrogen evolution reactions , 2017 .

[25]  Craig E Banks,et al.  Mass-Producible 2D-MoS2-Impregnated Screen-Printed Electrodes That Demonstrate Efficient Electrocatalysis toward the Oxygen Reduction Reaction. , 2017, ACS applied materials & interfaces.

[26]  H. Gasteiger,et al.  Analysis of Voltage Losses in PEM Water Electrolyzers with Low Platinum Group Metal Loadings , 2017 .

[27]  M. Ramasamy,et al.  Efficient hydrogen evolution catalysis triggered by electrochemically anchored platinum nano-islands on functionalized-MWCNT , 2017 .

[28]  Christopher W. Foster,et al.  Mass-producible 2D-MoSe2 bulk modified screen-printed electrodes provide significant electrocatalytic performances towards the hydrogen evolution reaction , 2017 .

[29]  T. Imae,et al.  Hydrogen evolution reaction efficiency by low loading of platinum nanoparticles protected by dendrimers on carbon materials , 2016 .

[30]  D. A. Brownson,et al.  Defining the origins of electron transfer at screen-printed graphene-like and graphite electrodes: MoO2 nanowire fabrication on edge plane sites reveals electrochemical insights. , 2016, Nanoscale.

[31]  Chun‐Sing Lee,et al.  Hierarchical composite structure of few-layers MoS2 nanosheets supported by vertical graphene on carbon cloth for high-performance hydrogen evolution reaction , 2015 .

[32]  D. A. Brownson,et al.  2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction. , 2015, Nanoscale.

[33]  Shuangbao Wang,et al.  Electrocatalytic Hydrogen Evolution Reaction on Edges of a Few Layer Molybdenum Disulfide Nanodots. , 2015, ACS applied materials & interfaces.

[34]  Yanguang Li,et al.  Ultrathin WS2 nanoflakes as a high-performance electrocatalyst for the hydrogen evolution reaction. , 2014, Angewandte Chemie.

[35]  C. Frost,et al.  Robust and reusable supported palladium catalysts for cross-coupling reactions in flow , 2014 .

[36]  A. K. Tyagi,et al.  Evolution and defect analysis of vertical graphene nanosheets , 2014, 1402.2074.

[37]  Shuhei Takahashi,et al.  Vertical graphene by plasma-enhanced chemical vapor deposition: Correlation of plasma conditions and growth characteristics , 2014 .

[38]  M. Batzill,et al.  Charge doping of graphene in metal/graphene/dielectric sandwich structures evaluated by C-1s core level photoemission spectroscopy , 2013 .

[39]  S. Dahl,et al.  Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot , 2012 .

[40]  Yongyou Hu,et al.  Iron- and nitrogen-functionalized graphene as a non-precious metal catalyst for enhanced oxygen reduction in an air-cathode microbial fuel cell , 2012 .

[41]  K. Mayrhofer,et al.  Time and potential resolved dissolution analysis of rhodium using a microelectrochemical flow cell coupled to an ICP-MS , 2012 .

[42]  Cinzia Casiraghi,et al.  Probing the nature of defects in graphene by Raman spectroscopy. , 2012, Nano letters.

[43]  J. Robertson,et al.  Metal‐Free Growth of Nanographene on Silicon Oxides for Transparent Conducting Applications , 2012 .

[44]  Hyunjoon Lee,et al.  A distinct platinum growth mode on shaped gold nanocrystals. , 2012, Chemical communications.

[45]  N. Soin,et al.  Microstructural and electrochemical properties of vertically aligned few layered graphene (FLG) nanoflakes and their application in methanol oxidation , 2011 .

[46]  D. Manos,et al.  Enhanced field emission of vertically oriented carbon nanosheets synthesized by C2H2/H2 plasma enhanced CVD , 2011 .

[47]  Jianguo Liu,et al.  Preparation and characterization of Pt supported on graphene with enhanced electrocatalytic activity in fuel cell , 2011 .

[48]  R. Li,et al.  A highly durable platinum nanocatalyst for proton exchange membrane fuel cells: multiarmed starlike nanowire single crystal. , 2011, Angewandte Chemie.

[49]  Yuyan Shao,et al.  Highly durable graphene nanoplatelets supported Pt nanocatalysts for oxygen reduction , 2010 .

[50]  O. Akhavan The effect of heat treatment on formation of graphene thin films from graphene oxide nanosheets , 2010 .

[51]  Zhenhua Ni,et al.  Probing layer number and stacking order of few-layer graphene by Raman spectroscopy. , 2010, Small.

[52]  Sarnjeet S. Dhesi,et al.  Catalyst‐Free Efficient Growth, Orientation and Biosensing Properties of Multilayer Graphene Nanoflake Films with Sharp Edge Planes , 2008 .

[53]  Chris Van Haesendonck,et al.  Field emission from vertically aligned few-layer graphene , 2008 .

[54]  Koen Schouteden,et al.  Synthesis of few-layer graphene via microwave plasma-enhanced chemical vapour deposition , 2008, Nanotechnology.

[55]  Zhiyong Zhang,et al.  C–H bond formation at the graphite surface studied with core level spectroscopy , 2008 .

[56]  S. Latil,et al.  Massless fermions in multilayer graphitic systems with misoriented layers: Ab initio calculations an , 2007, 0709.2315.

[57]  A. Ferrari,et al.  Raman spectroscopy of graphene and graphite: Disorder, electron phonon coupling, doping and nonadiabatic effects , 2007 .

[58]  Andre K. Geim,et al.  Raman spectrum of graphene and graphene layers. , 2006, Physical review letters.

[59]  C. Hierold,et al.  Spatially resolved Raman spectroscopy of single- and few-layer graphene. , 2006, Nano letters.

[60]  S. Machado,et al.  Study of hydrogen evolution reaction in acid medium on Pt microelectrodes , 2001 .

[61]  José Miguel Doña Rodríguez,et al.  Determination of the Real Surface Area of Pt Electrodes by Hydrogen Adsorption Using Cyclic Voltammetry , 2000 .

[62]  C. Teijeiro,et al.  An Electrochemistry Experiment: Hydrogen Evolution Reaction on Different Electrodes , 1994 .

[63]  Richard S. Nicholson,et al.  Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. , 1965 .

[64]  Christopher W. Foster,et al.  Single step additive manufacturing (3D printing) of electrocatalytic anodes and cathodes for efficient water splitting , 2020, Sustainable Energy & Fuels.

[65]  F. M. Sapountzi,et al.  Electrocatalysts for the generation of hydrogen, oxygen and synthesis gas , 2017 .

[66]  Jingzheng Ren,et al.  Introduction of Hydrogen Routines , 2017 .

[67]  Bo Z. Xu,et al.  Bimetallic Cobalt‐Based Phosphide Zeolitic Imidazolate Framework: CoPx Phase‐Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting , 2017 .

[68]  S. Nam,et al.  Anion exchange membrane water electrolyzer with an ultra-low loading of Pt-decorated Ni electrocatalyst , 2016 .

[69]  D. Manos,et al.  Synthesis of carbon nanosheets by inductively coupled radio-frequency plasma enhanced chemical vapor deposition , 2004 .