Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Journal Article · · Macromolecular Chemistry and Physics
ORCiD logo [1];  [2];  [3];  [2];  [2]; ORCiD logo [2]
  1. Cornell Univ., Ithaca, NY (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  2. Cornell Univ., Ithaca, NY (United States)
  3. Cornell Univ., Ithaca, NY (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
+ Show Author Affiliations

Abstract Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co‐assembly combined with non‐solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co‐assembly and non‐solvent‐induced phase separation (CNIPS) of poly(isoprene)‐ b ‐poly(styrene)‐ b ‐poly(4‐vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO 2 ) sol‐gel nanoparticlesare reported. Heat‐treatment in air results in free‐standing asymmetric porous TiO 2 . Further thermal processing in ammonia results in free‐standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross‐sections ( finger‐like to sponge‐like). Oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase‐pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy Solutions (CABES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-76SF00515; DMR-1707836; SC0019445
OSTI ID:
2006628
Alternate ID(s):
OSTI ID: 1894724
Journal Information:
Macromolecular Chemistry and Physics, Vol. 224, Issue 3; ISSN 1022-1352
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (45)

One-Pot Synthesis of Hierarchically Macro- and Mesoporous Carbon Materials with Graded Porosity journal April 2015
Carbon–Sulfur Composites from Cylindrical and Gyroidal Mesoporous Carbons with Tunable Properties in Lithium–Sulfur Batteries journal April 2015
Mechanism of Titania Deposition into Cylindrical Poly(styrene- block -4 vinyl pyridine) Block Copolymer Templates journal November 2011
Materials Combining Asymmetric Pore Structures with Well-Defined Mesoporosity for Energy Storage and Conversion journal November 2020
Block copolymer based composition and morphology control in nanostructured hybrid materials for energy conversion and storage: solar cells, batteries, and fuel cells journal January 2011
Hierarchically Porous Materials from Block Copolymers journal September 2013
True Performance Metrics in Electrochemical Energy Storage journal November 2011
Synthesis of Arrayed, TiO 2 Needlelike Nanostructures via a Polystyrene- block -poly(4-vinylpyridine) Diblock Copolymer Template journal September 2004
Synthesis and Characterization of Gyroidal Mesoporous Carbons and Carbon Monoliths with Tunable Ultralarge Pore Size journal December 2013
Phase Inversion: A Universal Method to Create High-Performance Porous Electrodes for Nanoparticle-Based Energy Storage Devices journal October 2016
Study of polymer concentration and evaporation time as phase inversion parameters for polysulfone-based SRNF membranes journal September 2013
Three-Dimensional Battery Architectures journal October 2004
Explaining the Enhanced Photocatalytic Activity of Degussa P25 Mixed-Phase TiO 2 Using EPR journal May 2003
Structurally Asymmetric Porous Carbon Materials with Ordered Top Surface Layers from Nonequilibrium Block Copolymer Self-Assembly journal March 2021
Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors journal January 2016
Asymmetric Organic–Inorganic Hybrid Membrane Formation via Block Copolymer–Nanoparticle Co-Assembly journal October 2013
Control of Solid-State Dye-Sensitized Solar Cell Performance by Block-Copolymer-Directed TiO2 Synthesis journal April 2010
New comprehensions on structure superiority of asymmetric carbon membrane and controlled construction of advanced hierarchical inner-structure for high performance supercapacitors journal February 2019
Networked and chiral nanocomposites from ABC triblock terpolymer coassembly with transition metal oxide nanoparticles journal January 2012
Effect of humidity on surface structure and permeation of triblock terpolymer derived SNIPS membranes journal September 2017
Multifunctional 3D nanoarchitectures for energy storage and conversion journal January 2009
Asymmetric superstructure formed in a block copolymer via phase separation journal November 2007
Where Do Batteries End and Supercapacitors Begin? journal March 2014
Direct access to thermally stable and highly crystalline mesoporous transition-metal oxides with uniform pores journal January 2008
Activated hierarchical porous carbon as electrode membrane accommodated with triblock copolymer for supercapacitors journal September 2016
Promises and challenges of nanomaterials for lithium-based rechargeable batteries journal June 2016
Nanostructured materials for advanced energy conversion and storage devices journal May 2005
Mesoporous titanium and niobium nitrides as conductive and stable electrocatalyst supports in acid environments journal January 2017
Efficient titanium nitride/titanium oxide composite photoanodes for dye-sensitized solar cells and water splitting journal January 2015
Monolithic Gyroidal Mesoporous Mixed Titanium–Niobium Nitrides journal July 2014
Nanomaterials for Rechargeable Lithium Batteries book January 2016
Crystalline Mixed Phase (Anatase/Rutile) Mesoporous Titanium Dioxides for Visible Light Photocatalytic Activity journal December 2014
Adsorption of Gases in Multimolecular Layers journal February 1938
A Simple Sol−Gel Processing for the Development of High-Temperature Stable Photoactive Anatase Titania journal August 2007
Selective Separation of Similarly Sized Proteins with Tunable Nanoporous Block Copolymer Membranes journal December 2012
Understanding the structure and performance of self-assembled triblock terpolymer membranes journal October 2013
Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage journal December 2015
Tuning Structure and Properties of Graded Triblock Terpolymer-Based Mesoporous and Hybrid Films journal July 2011
Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) journal January 1985
Tuning substructure and properties of supported asymmetric triblock terpolymer membranes journal December 2016
EPR Investigation of TiO2 Nanoparticles with Temperature-Dependent Properties
  • Kumar, Chinthala Praveen; Gopal, Neeruganti Obularajugari; Wang, Ting Chung
  • The Journal of Physical Chemistry B, Vol. 110, Issue 11 https://doi.org/10.1021/jp057053t
journal February 2006
Nonequilibrium Processes in Polymer Membrane Formation: Theory and Experiment journal May 2021
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms journal January 1951
Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores journal January 1998
Silver doped titanium dioxide nanomaterials for enhanced visible light photocatalysis journal June 2007

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
asymmetric structure
porous
sol gel
titanium nitride
titanium oxide