DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Effects of Atomic-Layer-Deposition Alumina on Proton Transmission through Single-Layer Graphene in Electrochemical Hydrogen Pump Cells

Journal Article · · ACS Applied Energy Materials

Fifty atomic layer deposition (ALD) cycles of trimethylaluminum and water were applied to single-layer graphene on copper and graphene on Nafion® membranes that result in alumina coatings that fully block photoelectron emission from the underlying substrate materials (copper and Nafion® respectively). This finding is consistent with relatively uninhibited alumina ALD nucleation and growth to a thickness of ~5 nm and further suggests that the alumina layer is continuous with no uncoated regions exposed. The ALD-derived alumina coatings are good barriers to large ions, e.g. from aqueous ferric chloride, but they have a relatively modest effect on proton transmission through graphene as measured in electrochemical hydrogen pump cell experiments. Proton currents of approximately 0.5 A cm-2 were obtained through Nafion® / graphene / ALD alumina / Nafion® at a modest bias voltage of 150 mV, which reflects a diminishment by less than half relative to the value for membranes without the 50 cycles of ALD alumina applied to the graphene. Proton transmission through the ALD alumina layer is thought to occur via hydrated alumina surfaces within the relatively porous ALD alumina layer on the graphene surface, and perhaps also at grain boundaries formed in the alumina during the ALD process.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1618436
Journal Information:
ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 2 Vol. 3; ISSN 2574-0962
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (67)

Escape Probability of Signal Auger and Photoelectrons from Ultrathin Overlayers journal August 1997
Recent Developments in Graphene-Based Membranes: Structure, Mass-Transport Mechanism and Potential Applications journal January 2016
Synthetic Two-Dimensional Materials: A New Paradigm of Membranes for Ultimate Separation journal May 2016
Nanoporous Atomically Thin Graphene Membranes for Desalting and Dialysis Applications journal June 2017
Atomic Layer Deposition for Graphene Device Integration journal May 2017
Characterization of gas crossover and its implications in PEM fuel cells journal January 2006
The Covalent Functionalization of Graphene on Substrates journal August 2015
Influences of Graphene Surface Treatment Temperature on a Growth of Al 2 O 3 Film by Atomic Layer Deposition on Graphene: Influences of Graphene Surface Treatment Temperature journal August 2017
Advanced analysis of copper X-ray photoelectron spectra: Advanced analysis of copper X-ray photoelectron spectra journal May 2017
Determination of attenuation lengths of photoelectrons in aluminium and aluminium oxide by angle-dependent x-ray photoelectron spectroscopy journal October 1993
Two-Dimensional Material Membranes: An Emerging Platform for Controllable Mass Transport Applications journal September 2014
Proton transfer and superionic conductivity in solids and gels journal July 1988
Calculation of inelastic mean free path of photoelectrons in some solids journal January 1988
Electrical conductivity of γ-Al2O3 at atmospheric pressure under dehydrating/hydrating conditions journal September 2001
Physical characterization of thin ALD–Al2O3 films journal April 2003
Surface refinement and electronic properties of graphene layers grown on copper substrate: An XPS, UPS and EELS study journal September 2011
Carbon nanomaterials for advancing separation membranes: A strategic perspective journal November 2016
A composite layer of atomic-layer-deposited Al2O3 and graphene for flexible moisture barrier journal May 2017
A comprehensive review on wettability, desalination, and purification using graphene-based materials at water interfaces journal October 2017
Carbon-nanostructures coated/decorated by atomic layer deposition: Growth and applications journal December 2013
A charge-transfer resistance model and Arrhenius activation analysis for hydrogen ion transmission across single-layer graphene journal February 2019
Pressurized PEM water electrolysis: Efficiency and gas crossover journal November 2013
Al2O3 coating grown on Nafion membranes by atomic layer deposition journal December 2015
Single Layer Graphene for Estimation of Axial Spatial Resolution in Confocal Raman Microscopy Depth Profiling journal December 2018
Enhanced Nucleation of High-k Dielectrics on Graphene by Atomic Layer Deposition journal October 2016
Uniform Atomic Layer Deposition of Al 2 O 3 on Graphene by Reversible Hydrogen Plasma Functionalization journal February 2017
Atomic Layer Deposition for Membranes: Basics, Challenges, and Opportunities journal October 2018
Graphene-Based Membranes for Molecular Separation journal July 2015
Hydrogenation Facilitates Proton Transfer through Two-Dimensional Honeycomb Crystals journal December 2017
Scalable Graphene-Based Membranes for Ionic Sieving with Ultrahigh Charge Selectivity journal January 2017
Partially Fluorinated Graphene: Structural and Electrical Characterization journal February 2016
Hydrophobic Surface Treatment and Interrupted Atomic Layer Deposition for Highly Resistive Al 2 O 3 Films on Graphene journal October 2016
Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene journal October 2016
Interface Electrical Properties of Al 2 O 3 Thin Films on Graphene Obtained by Atomic Layer Deposition with an in Situ Seedlike Layer journal February 2017
Ultrafast Nanofiltration through Large-Area Single-Layered Graphene Membranes journal March 2017
Single-Layer Graphene Sandwiched between Proton-Exchange Membranes for Selective Proton Transmission journal January 2019
Covalent Modification of Graphene and Graphite Using Diazonium Chemistry: Tunable Grafting and Nanomanipulation journal April 2015
Superpermeable Atomic-Thin Graphene Membranes with High Selectivity journal February 2017
Molecular Sieving Across Centimeter-Scale Single-Layer Nanoporous Graphene Membranes journal May 2017
Infrared and Gravimetric Study of the Surface Hydration of γ-Alumina journal January 1965
A Model for the Surface of γ-Alumina 1 journal January 1965
Basic Insights into Tunable Graphene Hydrogenation journal January 2016
Selective Proton/Deuteron Transport through Nafion|Graphene|Nafion Sandwich Structures at High Current Density journal January 2018
Possible Dual-Charge-Carrier Mechanism of Surface Conduction on γ-Alumina journal March 2007
Graphene Chemistry: Synthesis and Manipulation journal September 2011
Mechanisms of Molecular Permeation through Nanoporous Graphene Membranes journal January 2014
Properties of Fluorinated Graphene Films journal August 2010
Ultrathin Oxide Films by Atomic Layer Deposition on Graphene journal June 2012
Observing Graphene Grow: Catalyst–Graphene Interactions during Scalable Graphene Growth on Polycrystalline Copper journal September 2013
Fluorination of Graphene: A Spectroscopic and Microscopic Study journal January 2014
Proton transport through one-atom-thick crystals journal November 2014
Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping journal May 2017
Aqueous proton transfer across single-layer graphene journal March 2015
Water desalination using nanoporous single-layer graphene journal March 2015
Fundamental transport mechanisms, fabrication and potential applications of nanoporous atomically thin membranes journal June 2017
First principles study of the atomic layer deposition of alumina by TMA–H 2 O-process journal January 2015
Assessment and control of the impermeability of graphene for atomically thin membranes and barriers journal January 2017
Covalent chemistry on graphene journal January 2013
Structure of alumina surfaces journal January 1996
Measuring the proton selectivity of graphene membranes journal November 2015
Charging Behavior at the Alumina–Water Interface and Implications for Ceramic Processing journal November 2007
Review Article: Hydrogenated graphene: A user’s guide journal September 2018
Energy and material dependence of the inelastic mean free path of low‐energy electrons in solids journal May 1985
Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane journal January 2009
Sieving hydrogen isotopes through two-dimensional crystals journal December 2015
Transport Property Requirements for Flow Battery Separators journal July 2015
Coating strategies for atomic layer deposition journal November 2017