Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer
The prototypical [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) photosensitizer has been previously demonstrated to be labile in aqueous photocatalytic solutions, especially in the presence of coordinating electron donors. Here, an alternative RuII molecular sensitizer, [Ru(dpp)3]2+ (dpp=4,7-diphenyl-1,10-phena...
محفوظ في:
| المؤلف الرئيسي: | |
|---|---|
| مؤلفون آخرون: | , , |
| التنسيق: | article |
| منشور في: |
2016
|
| الوصول للمادة أونلاين: | http://hdl.handle.net/10725/6524 http://dx.doi.org/10.1002/cplu.201600227 http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php http://onlinelibrary.wiley.com/doi/10.1002/cplu.201600227/full |
| الوسوم: |
إضافة وسم
لا توجد وسوم, كن أول من يضع وسما على هذه التسجيلة!
|
| _version_ | 1864513480176959488 |
|---|---|
| author | Khnayzer, Rony S. |
| author2 | Olaiya, Babatunde S. El Roz, Karim A. Castellano, Felix N. |
| author2_role | author author author |
| author_facet | Khnayzer, Rony S. Olaiya, Babatunde S. El Roz, Karim A. Castellano, Felix N. |
| author_role | author |
| dc.creator.none.fl_str_mv | Khnayzer, Rony S. Olaiya, Babatunde S. El Roz, Karim A. Castellano, Felix N. |
| dc.date.none.fl_str_mv | 2016 2017-11-07T08:03:22Z 2017-11-07T08:03:22Z 2017-11-07 |
| dc.identifier.none.fl_str_mv | 2192-6506 http://hdl.handle.net/10725/6524 http://dx.doi.org/10.1002/cplu.201600227 Khnayzer, R. S., Olaiya, B. S., El Roz, K. A., & Castellano, F. N. (2016). Homogeneous Photocatalytic H2 Production Using a RuII Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer. ChemPlusChem, 81(10), 1090-1097. http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php http://onlinelibrary.wiley.com/doi/10.1002/cplu.201600227/full |
| dc.language.none.fl_str_mv | en |
| dc.relation.none.fl_str_mv | ChemPlusChem |
| dc.rights.*.fl_str_mv | info:eu-repo/semantics/openAccess |
| dc.title.none.fl_str_mv | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| dc.type.none.fl_str_mv | Article info:eu-repo/semantics/publishedVersion info:eu-repo/semantics/article |
| description | The prototypical [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) photosensitizer has been previously demonstrated to be labile in aqueous photocatalytic solutions, especially in the presence of coordinating electron donors. Here, an alternative RuII molecular sensitizer, [Ru(dpp)3]2+ (dpp=4,7-diphenyl-1,10-phenanthroline or bathophenanthroline), is described, which is considerably more stable than its bpy congener, allowing enhanced photocatalysis metrics in conjunction with a cobalt glyoxime ([Co(dmgH)2pyCl], dmgH=dimethylglyoxime, py=pyridine) water reduction catalyst and N,N-dimethyl-p-toluidine (DMT) as the sacrificial donor in a 1:1 mixture of CH3CN/H2O. Photoluminescence studies revealed that DMT reductively quenches the excited state of [Ru(dpp)3]2+ with a bimolecular rate constant of kq=4.9×109 m−1 s−1. The rate constant measured for electron transfer from the reduced sensitizer to the [Co(dmgH)2pyCl] was found to be near the diffusion limit, kCo=2.4×109 m−1 s−1. H2 production by photocatalysis was independently monitored by using a high-throughput photochemical reactor equipped with pressure transducers, gas chromatogram, and a mass spectrometer for detection; this illustrated that the composition yields high turnover numbers (TONs), approaching 10 000 (H2/Ru) with respect to the sensitizer and deuteration studies using D2O confirmed that H2 is primarily produced from protons derived from water in these systems. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | LAURepo_7201bd722b497ee9e44b301011ec2ccd |
| identifier_str_mv | 2192-6506 Khnayzer, R. S., Olaiya, B. S., El Roz, K. A., & Castellano, F. N. (2016). Homogeneous Photocatalytic H2 Production Using a RuII Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer. ChemPlusChem, 81(10), 1090-1097. |
| language_invalid_str_mv | en |
| network_acronym_str | LAURepo |
| network_name_str | Lebanese American University repository |
| oai_identifier_str | oai:laur.lau.edu.lb:10725/6524 |
| publishDate | 2016 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| spelling | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizerKhnayzer, Rony S.Olaiya, Babatunde S.El Roz, Karim A.Castellano, Felix N.The prototypical [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) photosensitizer has been previously demonstrated to be labile in aqueous photocatalytic solutions, especially in the presence of coordinating electron donors. Here, an alternative RuII molecular sensitizer, [Ru(dpp)3]2+ (dpp=4,7-diphenyl-1,10-phenanthroline or bathophenanthroline), is described, which is considerably more stable than its bpy congener, allowing enhanced photocatalysis metrics in conjunction with a cobalt glyoxime ([Co(dmgH)2pyCl], dmgH=dimethylglyoxime, py=pyridine) water reduction catalyst and N,N-dimethyl-p-toluidine (DMT) as the sacrificial donor in a 1:1 mixture of CH3CN/H2O. Photoluminescence studies revealed that DMT reductively quenches the excited state of [Ru(dpp)3]2+ with a bimolecular rate constant of kq=4.9×109 m−1 s−1. The rate constant measured for electron transfer from the reduced sensitizer to the [Co(dmgH)2pyCl] was found to be near the diffusion limit, kCo=2.4×109 m−1 s−1. H2 production by photocatalysis was independently monitored by using a high-throughput photochemical reactor equipped with pressure transducers, gas chromatogram, and a mass spectrometer for detection; this illustrated that the composition yields high turnover numbers (TONs), approaching 10 000 (H2/Ru) with respect to the sensitizer and deuteration studies using D2O confirmed that H2 is primarily produced from protons derived from water in these systems.PublishedN/A2017-11-07T08:03:22Z2017-11-07T08:03:22Z20162017-11-07Articleinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article2192-6506http://hdl.handle.net/10725/6524http://dx.doi.org/10.1002/cplu.201600227Khnayzer, R. S., Olaiya, B. S., El Roz, K. A., & Castellano, F. N. (2016). Homogeneous Photocatalytic H2 Production Using a RuII Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer. ChemPlusChem, 81(10), 1090-1097.http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.phphttp://onlinelibrary.wiley.com/doi/10.1002/cplu.201600227/fullenChemPlusCheminfo:eu-repo/semantics/openAccessoai:laur.lau.edu.lb:10725/65242021-03-19T10:03:27Z |
| spellingShingle | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer Khnayzer, Rony S. |
| status_str | publishedVersion |
| title | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| title_full | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| title_fullStr | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| title_full_unstemmed | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| title_short | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| title_sort | Homogeneous photocatalytic H2 production using a RuII bathophenanthroline metal-to-ligand charge-transfer photosensitizer |
| url | http://hdl.handle.net/10725/6524 http://dx.doi.org/10.1002/cplu.201600227 http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php http://onlinelibrary.wiley.com/doi/10.1002/cplu.201600227/full |