Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+
Abstract Frustrated Lewis pairs (FLPs) created by sterically hindered Lewis acids and Lewis bases have shown their capacity for capturing and reacting with a variety of small molecules, including H2 and CO2, and thereby creating a new strategy for CO2 reduction. Here, the photocatalytic CO2 reductio...
| Main Authors: | , , , , , , , , , , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2018-06-01
|
| Series: | Advanced Science |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/advs.201700732 |
| _version_ | 1797754222322647040 |
|---|---|
| author | Yuchan Dong Kulbir Kaur Ghuman Radian Popescu Paul N. Duchesne Wenjie Zhou Joel Y. Y. Loh Feysal M. Ali Jia Jia Di Wang Xiaoke Mu Christian Kübel Lu Wang Le He Mireille Ghoussoub Qiang Wang Thomas E. Wood Laura M. Reyes Peng Zhang Nazir P. Kherani Chandra Veer Singh Geoffrey A. Ozin |
| author_facet | Yuchan Dong Kulbir Kaur Ghuman Radian Popescu Paul N. Duchesne Wenjie Zhou Joel Y. Y. Loh Feysal M. Ali Jia Jia Di Wang Xiaoke Mu Christian Kübel Lu Wang Le He Mireille Ghoussoub Qiang Wang Thomas E. Wood Laura M. Reyes Peng Zhang Nazir P. Kherani Chandra Veer Singh Geoffrey A. Ozin |
| author_sort | Yuchan Dong |
| collection | DOAJ |
| description | Abstract Frustrated Lewis pairs (FLPs) created by sterically hindered Lewis acids and Lewis bases have shown their capacity for capturing and reacting with a variety of small molecules, including H2 and CO2, and thereby creating a new strategy for CO2 reduction. Here, the photocatalytic CO2 reduction behavior of defect‐laden indium oxide (In2O3−x(OH)y) is greatly enhanced through isomorphous substitution of In3+ with Bi3+, providing fundamental insights into the catalytically active surface FLPs (i.e., InOH···In) and the experimentally observed “volcano” relationship between the CO production rate and Bi3+ substitution level. According to density functional theory calculations at the optimal Bi3+ substitution level, the 6s2 electron pair of Bi3+ hybridizes with the oxygen in the neighboring InOH Lewis base site, leading to mildly increased Lewis basicity without influencing the Lewis acidity of the nearby In Lewis acid site. Meanwhile, Bi3+ can act as an extra acid site, serving to maximize the heterolytic splitting of reactant H2, and results in a more hydridic hydride for more efficient CO2 reduction. This study demonstrates that isomorphous substitution can effectively optimize the reactivity of surface catalytic active sites in addition to influencing optoelectronic properties, affording a better understanding of the photocatalytic CO2 reduction mechanism. |
| first_indexed | 2024-03-12T17:29:35Z |
| format | Article |
| id | doaj.art-457955f3586b45389c079055c2988fa8 |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-03-12T17:29:35Z |
| publishDate | 2018-06-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj.art-457955f3586b45389c079055c2988fa82023-08-05T03:41:20ZengWileyAdvanced Science2198-38442018-06-0156n/an/a10.1002/advs.201700732Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+Yuchan Dong0Kulbir Kaur Ghuman1Radian Popescu2Paul N. Duchesne3Wenjie Zhou4Joel Y. Y. Loh5Feysal M. Ali6Jia Jia7Di Wang8Xiaoke Mu9Christian Kübel10Lu Wang11Le He12Mireille Ghoussoub13Qiang Wang14Thomas E. Wood15Laura M. Reyes16Peng Zhang17Nazir P. Kherani18Chandra Veer Singh19Geoffrey A. Ozin20Department of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaDepartment of Materials Science and Engineering University of Toronto 184 College Street, Suite 140 Toronto Ontario M5S 3E4 CanadaLaboratory for Electron Microscopy (LEM) Karlsruhe Institute of Technology (KIT) Engesserstr. 7 76131 Karlsruhe GermanyDepartment of Chemistry Dalhousie University 6274 Coburg Road, P.O. Box 15000 Halifax B3H 4R2 CanadaDepartment of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaThe Edward S. Rogers Sr. Department of Electrical and Computer Engineering University of Toronto 10 King's College Road Toronto Ontario M5S 3G4 CanadaDepartment of Materials Science and Engineering University of Toronto 184 College Street, Suite 140 Toronto Ontario M5S 3E4 CanadaDepartment of Materials Science and Engineering University of Toronto 184 College Street, Suite 140 Toronto Ontario M5S 3E4 CanadaInstitute of Nanotechnology and Karlsruhe Nano Micro Facility Karlsruhe Institute of Technology Hermann‐von‐Helmholtz Platz 1 76344 Eggenstein‐Leopoldshafen GermanyHelmholtz‐Institute Ulm for Electrochemical Energy Storage (HIU) Karlsruhe Institute of Technology (KIT) 89081 Ulm GermanyInstitute of Nanotechnology and Karlsruhe Nano Micro Facility Karlsruhe Institute of Technology Hermann‐von‐Helmholtz Platz 1 76344 Eggenstein‐Leopoldshafen GermanyDepartment of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaInstitute of Functional Nano and Soft Materials (FUNSOM) Soochow University Suzhou 215123 Jiangsu ChinaDepartment of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaInstitute of Coal Chemistry Chinese Academy of Science 27 Taoyuan South Road Taiyuan 030001 Shanxi ChinaDepartment of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaDepartment of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaDepartment of Chemistry Dalhousie University 6274 Coburg Road, P.O. Box 15000 Halifax B3H 4R2 CanadaDepartment of Materials Science and Engineering University of Toronto 184 College Street, Suite 140 Toronto Ontario M5S 3E4 CanadaDepartment of Materials Science and Engineering University of Toronto 184 College Street, Suite 140 Toronto Ontario M5S 3E4 CanadaDepartment of Chemistry University of Toronto 80 St. George Street, Rm 326 Toronto Ontario M5S 3H6 CanadaAbstract Frustrated Lewis pairs (FLPs) created by sterically hindered Lewis acids and Lewis bases have shown their capacity for capturing and reacting with a variety of small molecules, including H2 and CO2, and thereby creating a new strategy for CO2 reduction. Here, the photocatalytic CO2 reduction behavior of defect‐laden indium oxide (In2O3−x(OH)y) is greatly enhanced through isomorphous substitution of In3+ with Bi3+, providing fundamental insights into the catalytically active surface FLPs (i.e., InOH···In) and the experimentally observed “volcano” relationship between the CO production rate and Bi3+ substitution level. According to density functional theory calculations at the optimal Bi3+ substitution level, the 6s2 electron pair of Bi3+ hybridizes with the oxygen in the neighboring InOH Lewis base site, leading to mildly increased Lewis basicity without influencing the Lewis acidity of the nearby In Lewis acid site. Meanwhile, Bi3+ can act as an extra acid site, serving to maximize the heterolytic splitting of reactant H2, and results in a more hydridic hydride for more efficient CO2 reduction. This study demonstrates that isomorphous substitution can effectively optimize the reactivity of surface catalytic active sites in addition to influencing optoelectronic properties, affording a better understanding of the photocatalytic CO2 reduction mechanism.https://doi.org/10.1002/advs.201700732carbon dioxideisomorphous substitutionphotocatalystssolar fuelssurface‐frustrated Lewis pairs |
| spellingShingle | Yuchan Dong Kulbir Kaur Ghuman Radian Popescu Paul N. Duchesne Wenjie Zhou Joel Y. Y. Loh Feysal M. Ali Jia Jia Di Wang Xiaoke Mu Christian Kübel Lu Wang Le He Mireille Ghoussoub Qiang Wang Thomas E. Wood Laura M. Reyes Peng Zhang Nazir P. Kherani Chandra Veer Singh Geoffrey A. Ozin Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+ Advanced Science carbon dioxide isomorphous substitution photocatalysts solar fuels surface‐frustrated Lewis pairs |
| title | Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+ |
| title_full | Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+ |
| title_fullStr | Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+ |
| title_full_unstemmed | Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+ |
| title_short | Tailoring Surface Frustrated Lewis Pairs of In2O3−x(OH)y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO2 by Isomorphous Substitution of In3+ with Bi3+ |
| title_sort | tailoring surface frustrated lewis pairs of in2o3 x oh y for gas phase heterogeneous photocatalytic reduction of co2 by isomorphous substitution of in3 with bi3 |
| topic | carbon dioxide isomorphous substitution photocatalysts solar fuels surface‐frustrated Lewis pairs |
| url | https://doi.org/10.1002/advs.201700732 |
| work_keys_str_mv | AT yuchandong tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT kulbirkaurghuman tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT radianpopescu tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT paulnduchesne tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT wenjiezhou tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT joelyyloh tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT feysalmali tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT jiajia tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT diwang tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT xiaokemu tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT christiankubel tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT luwang tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT lehe tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT mireilleghoussoub tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT qiangwang tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT thomasewood tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT lauramreyes tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT pengzhang tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT nazirpkherani tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT chandraveersingh tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 AT geoffreyaozin tailoringsurfacefrustratedlewispairsofin2o3xohyforgasphaseheterogeneousphotocatalyticreductionofco2byisomorphoussubstitutionofin3withbi3 |