Abstract
Silatrane surface anchors are protected siloxanes that are known to bond firmly (from pH 2-11) to metal oxide electrodes under heating. However, these conditions are not always compatible with the other functionality present. A silatrane-containing porphyrin molecule and a silatrane-containing ruthenium complex have now been designed, synthesized and optimized conditions have been identified for surface binding. Two mild, roomerature surface binding methods were explored: binding with or without an acidic pretreatment; these methods were compared to the traditional, harsher binding conditions involving strong heating. We find that a preacidified electrode gave comparable surface loadings at room temperature compared to sensitization by using the previous strong heating method. This was also true on TiO 2 , SnO 2 , and nanoITO electrodes and thus may be generalizable. The new, milder binding methods also resulted in excellent aqueous and electrochemical stability from pH 2-11. Using a water-insoluble porphyrin with a silatrane anchor further increased the aqueous stability of the deposit, aided by the insolubility of the porphyrin. Finally, X-ray photoelectron spectroscopy (XPS) data confirmed for the first time that the triethanolamine released from the silatrane on deprotection/binding in turn binds to TiO 2 , SnO 2 , and nanoITO electrodes. This undesired triethanolamine deposit was easily removed from the surface by electrochemical voltage cycling or with an aqueous acidic wash for 1 h.
| Original language | English |
|---|---|
| Pages (from-to) | 5602-5609 |
| Number of pages | 8 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 11 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Feb 13 2019 |
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Keywords
- metal oxides
- silatranes
- solar energy
- surface anchors
- tin oxide
- titanium dioxide
- water splitting
ASJC Scopus subject areas
- Materials Science(all)
Cite this
Silatrane Anchors for Metal Oxide Surfaces : Optimization for Potential Photocatalytic and Electrocatalytic Applications. / Materna, Kelly L.; Jiang, Jianbing; Crabtree, Robert H.; Brudvig, Gary W.
In: ACS Applied Materials and Interfaces, Vol. 11, No. 6, 13.02.2019, p. 5602-5609.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Silatrane Anchors for Metal Oxide Surfaces
T2 - Optimization for Potential Photocatalytic and Electrocatalytic Applications
AU - Materna, Kelly L.
AU - Jiang, Jianbing
AU - Crabtree, Robert H.
AU - Brudvig, Gary W
PY - 2019/2/13
Y1 - 2019/2/13
N2 - Silatrane surface anchors are protected siloxanes that are known to bond firmly (from pH 2-11) to metal oxide electrodes under heating. However, these conditions are not always compatible with the other functionality present. A silatrane-containing porphyrin molecule and a silatrane-containing ruthenium complex have now been designed, synthesized and optimized conditions have been identified for surface binding. Two mild, roomerature surface binding methods were explored: binding with or without an acidic pretreatment; these methods were compared to the traditional, harsher binding conditions involving strong heating. We find that a preacidified electrode gave comparable surface loadings at room temperature compared to sensitization by using the previous strong heating method. This was also true on TiO 2 , SnO 2 , and nanoITO electrodes and thus may be generalizable. The new, milder binding methods also resulted in excellent aqueous and electrochemical stability from pH 2-11. Using a water-insoluble porphyrin with a silatrane anchor further increased the aqueous stability of the deposit, aided by the insolubility of the porphyrin. Finally, X-ray photoelectron spectroscopy (XPS) data confirmed for the first time that the triethanolamine released from the silatrane on deprotection/binding in turn binds to TiO 2 , SnO 2 , and nanoITO electrodes. This undesired triethanolamine deposit was easily removed from the surface by electrochemical voltage cycling or with an aqueous acidic wash for 1 h.
AB - Silatrane surface anchors are protected siloxanes that are known to bond firmly (from pH 2-11) to metal oxide electrodes under heating. However, these conditions are not always compatible with the other functionality present. A silatrane-containing porphyrin molecule and a silatrane-containing ruthenium complex have now been designed, synthesized and optimized conditions have been identified for surface binding. Two mild, roomerature surface binding methods were explored: binding with or without an acidic pretreatment; these methods were compared to the traditional, harsher binding conditions involving strong heating. We find that a preacidified electrode gave comparable surface loadings at room temperature compared to sensitization by using the previous strong heating method. This was also true on TiO 2 , SnO 2 , and nanoITO electrodes and thus may be generalizable. The new, milder binding methods also resulted in excellent aqueous and electrochemical stability from pH 2-11. Using a water-insoluble porphyrin with a silatrane anchor further increased the aqueous stability of the deposit, aided by the insolubility of the porphyrin. Finally, X-ray photoelectron spectroscopy (XPS) data confirmed for the first time that the triethanolamine released from the silatrane on deprotection/binding in turn binds to TiO 2 , SnO 2 , and nanoITO electrodes. This undesired triethanolamine deposit was easily removed from the surface by electrochemical voltage cycling or with an aqueous acidic wash for 1 h.
KW - metal oxides
KW - silatranes
KW - solar energy
KW - surface anchors
KW - tin oxide
KW - titanium dioxide
KW - water splitting
UR - http://www.scopus.com/inward/record.url?scp=85061565833&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85061565833&partnerID=8YFLogxK
U2 - 10.1021/acsami.8b04138
DO - 10.1021/acsami.8b04138
M3 - Article
VL - 11
SP - 5602
EP - 5609
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
SN - 1944-8244
IS - 6
ER -