Elucidation of the Effect of Functional Group Substitution of BN-cyclohexane for Renewable Energy Hydrogen Storage: Density Functional Theory Approach

Govindaraja Senthamaraikannan Thillai; Dong-Hee Lim

doi:10.32390/ksmer.2022.59.1.021

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2022 Vol.59, Issue 1 Preview Page Next Page

Research Paper

Elucidation of the Effect of Functional Group Substitution of BN-cyclohexane for Renewable Energy Hydrogen Storage: Density Functional Theory Approach 신재생에너지 수소 저장을 위한 BN-cyclohexane 기능기 치환 효과 규명: 밀도범함수이론 연구

28 February 2022. pp. 21-30

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Abstract

Liquid organic hydrogen carrier (LOHC) has been attracting attention as a hydrogen storage technology. Among the LOHC materials, we explore fluorine (F) and amine (NH₂) functional group substituted 1,2-BN cyclohexane-based hydrogen storage materials with improved reversibility of dehydrogenation-hydrogenation reaction. Density functional theory (DFT) calculations were conducted by using Gaussian 16 software to calculate dehydrogenation reaction enthalpy (∆H) and reaction free energy (∆G). F-BN-cyclohexane and NH₂-BN-cyclohexane show ∆G of ‒4.10 and ‒5.38 kJ/mol, respectively, whereas 1,2-BN cyclohexane shows ∆G of ‒5.71 kJ/mol. Because the reversibility of dehydrogenation-hydrogenation reactions is excellent as the ∆G value is close to zero, the functional group substitution enhanced the reversibility of the dehydrogenation-hydrogenation reaction. This DFT study not only presents a systematic methodology to evaluate the dehydrogenation-hydrogenation reaction reversibility that can be improved by substituting F and NH₂ functional groups in existing BN-cyclohexane, but also provides the fundamental mechanisms of dehydrogenation of F- and NH₂-BN-cyclohexane.

Keywords

Hydrogen storage

Liquid organic hydrogen carrier (LOHC)

Dehydrogenation

Hydrogenation

Density functional theory (DFT)

액상유기수소운반체(liquid organic hydrogen carrier, LOHC)는 액상 형태로 수소를 효율적으로 저장 및 방출할 수 있는 물질로서 미래 수소경제 활성화에 있어서 효과적 수소 저장 물질로 주목받고 있다. 그 중 1,2-BN-cyclohexane 물질은 열역학적으로 안정하며 상온에서의 탈수소화 반응 시 휘발성 오염물질을 방출하지 않는 장점을 가지고 있다. 본 연구에서는 밀도범함수이론(density functional theory, DFT) 계산을 활용하여 1,2-BN-cyclohexane 물질에 기능기 F 및 NH₂를 치환하여 더 향상된 가역적 수소 저장 물질로서의 가능성을 평가하고자 하였다. 1,2-BN-cyclohexane 물질의 탈수소화 ∆G는 ‒5.71 kJ/mol인 반면, F-BN-cyclohexane과 NH₂-BN-cyclohexane의 탈수소화 ∆G는 각각 ‒4.10과 ‒5.38 kJ/mol으로 나타났다. 탈수소화 ∆G 값이 0 (zero)에 가까울수록 더 가역적인 탈수소화-수소화 반응임을 고려할 때, F와 NH₂ 기능기로써 치환된 BN-cyclohexane 물질의 가역성이 기존 물질보다 더 향상될 수 있음을 보여주었다. 본 밀도범함수이론(DFT) 연구는 기존 BN-cyclohexane 물질에서 F와 NH₂ 기능기를 치환함에 따라 향상될 수 있는 탈수소화-수소화 가역적 반응성을 평가하는 체계적 방법론을 제시할 뿐만 아니라, 기존 BN-cyclohexane 물질보다 더 향상된 탈수소화-수소화 반응 가역성을 나타낼 수 있는F-BN-cyclohexane 물질의 제안과 반응 메커니즘에 대한 자세한 정보를 제공해준다.

키워드

수소저장

액상유기수소운반체

탈수소화

수소화

밀도범함수이론

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Information

Publisher :The Korean Society of Mineral and Energy Resources Engineers
Publisher(Ko) :한국자원공학회
Journal Title :Journal of the Korean Society of Mineral and Energy Resources Engineers
Journal Title(Ko) :한국자원공학회지
Volume : 59
No :1
Pages :21-30
Received Date : 2022-01-12
Revised Date : 2022-01-21
Accepted Date : 2022-02-22
DOI :https://doi.org/10.32390/ksmer.2022.59.1.021

Journal of the Korean Society of Mineral and Energy Resources Engineers ISSN:2288-0291(Print) 2288-2790(Online) 한국자원공학회지

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