What Is the Best Size of Subnanometer Copper Clusters for CO2 Conversion to Methanol at Cu/TiO2 Interfaces? A Density Functional Theory Study - Details

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Abstract：

The　activation　and　hydrogenation　of　CO2　at　the　Cu/TiO2　interfaces　that　are　formed　by　depositing　subnanometer　Cun　(n　=　1-8)　clusters　on　TiO2(110)　surfaces　have　been　systematically　investigated　using　density　functional　theory　calculations.　The　most　stable　structures　with　a　bent　CO2　δ-　configuration　at　the　Cun/TiO2　interfaces　are　determined,　which　indicate　that　the　binding　strength　of　CO2　on　the　Cun/TiO2(110)　surface　can　be　tuned　by　controlling　the　size　of　the　deposited　Cu　cluster.　It　is　interesting　that　the　copper　cluster　with　a　specific　size　of　Cu4　exhibits　a　distinct　preference　for　CO2　activation,　and　the　strongest　binding　interaction　between　CO2　and　Cu4/TiO2(110)　is　mainly　ascribed　to　the　formation　of　the　strong　Cu-C　and　Ti-O　adsorption　bonds.　The　reaction　mechanisms　of　CO2　conversion　to　CH3OH　at　the　Cu4/TiO2(110)　interface　via　the　formate　and　the　reverse　water　gas　shift　(RWGS)　+　CO-hydrogenation　pathways　are　further　investigated　by　microkinetic　simulations.　The　production　of　CH3OH　over　Cu4/TiO2　is　mainly　via　the　RWGS　pathway　to　yield　CO　followed　by　the　formation　of　H3CO∗　as　the　most　stable　intermediate,　while　the　formate　pathway　is　not　efficient　enough　because　of　the　higher　apparent　activation　energy　of　CH3OH　generation　and　the　overly　strong　binding　of　HCOO∗　species　at　the　interface.　Compared　with　other　Cun/TiO2　interfaces,　the　TiO2(110)　surface-supported　size-selected　Cu4　cluster　exhibits　the　highest　CO2　hydrogenation　activity.　The　findings　obtained　in　the　present　work　provide　useful　insight　to　design　Cu/oxide　interfaces　with　high　activity　toward　methanol　synthesis　from　CO2　hydrogenation　by　precisely　controlling　the　size　of　copper　clusters.　©　2019　American　Chemical　Society.

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[ 1 ] [Tao, H.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 2 ] [Li, Y.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 3 ] [Cai, X.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 4 ] [Zhou, H.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 5 ] [Zhou, H.]College of Chemical and Biological Engineering, Yichun University, Yichun, Jiangxi, 336000, China
[ 6 ] [Li, Y.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 7 ] [Li, Y.]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen, Fujian, 361005, China
[ 8 ] [Lin, W.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 9 ] [Lin, W.]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen, Fujian, 361005, China
[ 10 ] [Huang, S.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 11 ] [Huang, S.]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen, Fujian, 361005, China
[ 12 ] [Ding, K.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 13 ] [Ding, K.]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen, Fujian, 361005, China
[ 14 ] [Chen, W.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 15 ] [Chen, W.]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen, Fujian, 361005, China
[ 16 ] [Zhang, Y.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China
[ 17 ] [Zhang, Y.]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen, Fujian, 361005, China

Reprint 's Address：

[Li, Y.]State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou UniversityChina

Email：

liy99@fzu.edu.cn

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Source ：

Journal of Physical Chemistry C

ISSN： 1932-7447

Year： 2019

Issue： 39

Volume： 123

Page： 24118-24132

4 . 1 8 9

JCR@2019

3 . 3 0 0

JCR@2023

ESI HC Threshold：184

JCR Journal Grade：2

CAS Journal Grade：3

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SCOPUS Cited Count： 41

ESI Highly Cited Papers on the List： 0 Unfold All

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30 Days PV： 0

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