酸化グラフェンのシートサイズが希土類元素の分離を制御(Graphene Oxide Sheet Size Controls Rare Earth Element Separations)

2025-08-11 パシフィック・ノースウェスト国立研究所(PNNL)

米国PNNLの研究で、グラフェンオキサイド(GO)シートのサイズが希土類元素分離性能に大きく影響することが判明した。小型シート(約0.6~0.8µm)は大型(約1µm)よりユーロピウム(Eu³⁺)の吸着容量が高く、透過速度が低い。これは拡散経路の違い(小型は垂直細孔が多く、大型は層間チャネル主体)、小型シートエッジのカルボキシラート基とEu³⁺の強い静電相互作用、酸素含有基との結合エネルギー差によるもの。本知見は膜・吸着材設計において、微細構造や化学特性の調整が性能最適化に有効であることを示し、効率的な希土類分離技術開発の指針となる。

<関連情報>

グラフェン酸化物シートのサイズは、ラミネート膜のイオン吸着と透過挙動に影響を与える Graphene oxide sheet size influences the ion adsorption and permeation behavior of laminate membranes

Shuai Tan, Samantha Reid, Manh Thuong Nguyen, Elaf A. Anber, Daniel Foley, Richard Shiery, Vaithiyalingam Shutthanandan, Mark E. Bowden, Mitra Taheri, Heriberto Hernandez, Venkateshkumar Prabhakaran, Grant E. Johnson
Carbon  Available online: 2 April 2025
DOI:https://doi.org/10.1016/j.carbon.2025.120280

Graphical abstract

Ion diffusion channels, including vertical and horizontal channels, through the laminar structure of GO.

酸化グラフェンのシートサイズが希土類元素の分離を制御(Graphene Oxide Sheet Size Controls Rare Earth Element Separations)

Abstract

We utilized size fractionation along with ion adsorption and permeation measurements, microscopy and spectroscopy characterization, and theoretical calculations to understand the role of graphene oxide (GO) sheet size and functionality in metal ion separations, focusing on europium cations (Eu3+) as a model system. Our findings reveal that even though different-sized GO sheets exhibit subtle differences in their chemical and physical properties, adsorbents and membranes assembled from GO flakes of various sizes display size-dependent ion adsorption capacities and permeation rates. Specifically, GO adsorbents and membranes comprised of smaller ∼0.6 and 0.8 μm diameter GO sheets exhibit higher Eu3+ adsorption capacities and lower permeation rates compared to those assembled from larger ∼1.0 μm GO sheets. Detailed experimental analysis and theoretical simulations suggest that this phenomenon may be attributed to three competing factors: 1) a shift of the primary Eu3+ diffusion pathway from the horizontal interlayer transport channels between larger vertically stacked GO sheets to the more numerous vertical pores between smaller adjacent GO sheets in nearby planes, 2) Coulombic effects induced by strong electrostatic interactions between carboxylate groups (–COO) located at the edges of smaller GO sheets and Eu3+ cations, and 3) the different binding energies between specific oxygen functional groups on GO and Eu3+. Understanding the role of the dimensions and chemical functionality of GO sheets in determining selective ion adsorption and transport provides useful insight to guide the rational design of improved adsorbents and membranes, opening up new opportunities for the separation of critical materials, including rare-earth elements.

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