Scalable Bottom-Up Synthesis of Nanoporous Hexagonal Boron Nitride (h-BN) for Large-Area Atomically Thin Ceramic Membranes

Published

February 14, 2025

Author(s)

Andrew Naclerio, Peifu Cheng, Saban Hus, John Diulus, Marti Checa, Ivan Vlassiouk, William Fissel, Liam Collins, Matthew Coupin, Jamie Warner, Andrei Kolmakov, An-Ping Li, Piran Ravichandran Kidambi

Abstract

Nanopores embedded within monolayer hexagonal boron nitride (h-BN) offer possibilities of creating atomically thin ceramic membranes with unique combinations of high permeance (atomic thinness), high selectivity (via molecular sieving), increased thermal stability and superior chemical resistance. However, fabricating size-selective nanopores in monolayer h-BN via scalable top-down processes remains non-trivial due to its chemical inertness and characterizing nanopore size distribution over large area remains extremely challenging. Here, we demonstrate a facile and scalable approach of exploiting the chemical vapor deposition (CVD) process temperature to enable direct incorporation of sub-nanometer/nanoscale pores into the monolayer h-BN lattice, in combination with manufacturing compatible polymer casting to fabricate centimeter-scale nanoporous atomically thin ceramic membranes. We leverage diffusive-transport of analytes including size-selective Ficoll sieving to characterize sub-nanometer and nanoscale defects that manifest as pores in centimeter-scale h-BN membranes, overcoming previous limitations in large-area characterization of nanoscale defects in h-BN. Finally, we demonstrate functional lab-scale nanoporous atomically-thin h-BN membranes with separation factors 97 for KCl (0.66nm)/Lysozyme (3.8-4nm) and 43 for L-tryptophan (0.7-0.9nm)/Lysozyme with high permeance (KCl 7.410-6 ms-1, L-Tr 3.310-6 ms-1, Vitamin B12 1.210-6 ms-1) for model nanoscale separations i.e. protein-desalting/dialysis/small-molecule separation. Our approach opens a new frontier to advance atomically thin membranes to 2D ceramic materials, such as h-BN via facile and direct formation of nanopores, for size-selective separations

Citation

Nano Letters

Volume

25

Issue

8

Pub Type

Journals

Download Paper

https://doi.org/10.1021/acs.nanolett.4c05939

Local Download

Keywords

hexagonal boron nitride (h-BN), chemical vapor deposition (CVD), h-BN membranes, ceramic membranes, nanoporous atomically thin membranes, nanopores, defects in h-BN

Citation

Naclerio, A. , Cheng, P. , Hus, S. , Diulus, J. , Checa, M. , Vlassiouk, I. , Fissel, W. , Collins, L. , Coupin, M. , Warner, J. , Kolmakov, A. , Li, A. and Kidambi, P. (2025), Scalable Bottom-Up Synthesis of Nanoporous Hexagonal Boron Nitride (h-BN) for Large-Area Atomically Thin Ceramic Membranes, Nano Letters, [online], https://doi.org/10.1021/acs.nanolett.4c05939, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=959047 (Accessed October 6, 2025)