Abstract
A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated planar glassy carbon electrode surface. Coupling proceeds with both the Ni(0) and the Ni(II) complexes. X-ray photoemission spectra show excellent agreement between the Ni(0) coupling product and its parent complex, and voltammetry of the surface-confined system shows that a single species predominates with a surface density of 1.3 × 10-10 mol cm-2, approaching the value estimated for a densely packed monolayer. With the Ni(II) system, both photoemission and voltammetric data show speciation to unidentified products on coupling, and the surface density is 6.7 × 10-11 mol cm-2. The surface-confined Ni(0) complex is an electroctalyst for hydrogen evolution, showing the onset of catalytic current at the same potential as the soluble parent complex. Decomposition of the surface-confined species is observed in acidic acetonitrile. This is interpreted to reflect the lability of the Ni(II)-phosphine interaction and the basicity of the free phosphine and bears on concurrent efforts to implement surface-confined Ni(P2N 2)2 complexes in electrochemical or photoelectrochemical devices.
| Original language | English |
|---|---|
| Pages (from-to) | 6875-6885 |
| Number of pages | 11 |
| Journal | Inorganic Chemistry |
| Volume | 53 |
| Issue number | 13 |
| DOIs | |
| Publication status | Published - Jul 7 2014 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
A hydrogen-evolving Ni(P2N2)2 electrocatalyst covalently attached to a glassy carbon electrode : Preparation, characterization, and catalysis. Comparisons with the homogeneous analogue. / Das, Atanu K.; Engelhard, Mark H.; Bullock, R Morris; Roberts, John.
In: Inorganic Chemistry, Vol. 53, No. 13, 07.07.2014, p. 6875-6885.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - A hydrogen-evolving Ni(P2N2)2 electrocatalyst covalently attached to a glassy carbon electrode
T2 - Preparation, characterization, and catalysis. Comparisons with the homogeneous analogue
AU - Das, Atanu K.
AU - Engelhard, Mark H.
AU - Bullock, R Morris
AU - Roberts, John
PY - 2014/7/7
Y1 - 2014/7/7
N2 - A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated planar glassy carbon electrode surface. Coupling proceeds with both the Ni(0) and the Ni(II) complexes. X-ray photoemission spectra show excellent agreement between the Ni(0) coupling product and its parent complex, and voltammetry of the surface-confined system shows that a single species predominates with a surface density of 1.3 × 10-10 mol cm-2, approaching the value estimated for a densely packed monolayer. With the Ni(II) system, both photoemission and voltammetric data show speciation to unidentified products on coupling, and the surface density is 6.7 × 10-11 mol cm-2. The surface-confined Ni(0) complex is an electroctalyst for hydrogen evolution, showing the onset of catalytic current at the same potential as the soluble parent complex. Decomposition of the surface-confined species is observed in acidic acetonitrile. This is interpreted to reflect the lability of the Ni(II)-phosphine interaction and the basicity of the free phosphine and bears on concurrent efforts to implement surface-confined Ni(P2N 2)2 complexes in electrochemical or photoelectrochemical devices.
AB - A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated planar glassy carbon electrode surface. Coupling proceeds with both the Ni(0) and the Ni(II) complexes. X-ray photoemission spectra show excellent agreement between the Ni(0) coupling product and its parent complex, and voltammetry of the surface-confined system shows that a single species predominates with a surface density of 1.3 × 10-10 mol cm-2, approaching the value estimated for a densely packed monolayer. With the Ni(II) system, both photoemission and voltammetric data show speciation to unidentified products on coupling, and the surface density is 6.7 × 10-11 mol cm-2. The surface-confined Ni(0) complex is an electroctalyst for hydrogen evolution, showing the onset of catalytic current at the same potential as the soluble parent complex. Decomposition of the surface-confined species is observed in acidic acetonitrile. This is interpreted to reflect the lability of the Ni(II)-phosphine interaction and the basicity of the free phosphine and bears on concurrent efforts to implement surface-confined Ni(P2N 2)2 complexes in electrochemical or photoelectrochemical devices.
UR - http://www.scopus.com/inward/record.url?scp=84903977886&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84903977886&partnerID=8YFLogxK
U2 - 10.1021/ic500701a
DO - 10.1021/ic500701a
M3 - Article
AN - SCOPUS:84903977886
VL - 53
SP - 6875
EP - 6885
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 13
ER -