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Scalable one-step assembly of an inexpensive photoelectrode for water oxidation by deposition of a Ti- and Ni-containing molecular precursor on nanostructured WO3.

Lai YH, King TC, Wright DS, Reisner E - Chemistry (2013)

Bottom Line: Photoactive in one step!A nanocomposite water-oxidation photocatalyst was assembled by a straightforward and one-step spin-coating procedure of a Ti- and Ni-containing molecule on nanostructured WO3.The photoanode oxidizes water to O2 with good activity and stability in alkaline solution, and thereby features light absorption, charge separation and water-oxidation catalysis (see scheme).

View Article: PubMed Central - PubMed

Affiliation: Christian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (UK).

No MeSH data available.


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a) Consecutive cyclic voltammograms with FTO/TiNi in an aqueous Bi solution (0.1 m, pH 9.2) at RT and a scan rate of 50 mV s−1 showing the increase in the NiII/III oxidation wave9a, b at approximately Ep=1.62 V versus RHE and the wave for electrocatalytic water oxidation at an onset potential of approximately Ecat=1.73 V versus RHE. A platinum counter and a Ag/AgCl/KCl(sat) reference electrode were employed. b) Amount of O2 evolved during controlled potential electrolysis with FTO/TiNi under the same conditions at an applied potential of 2.0 V versus RHE between one and seven hours. The amount of O2 was quantified by an O2 fluorescence probe (solid trace) and the dashed trace shows the theoretical amount of O2 calculated based on 100 % Faradaic efficiency.
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fig02: a) Consecutive cyclic voltammograms with FTO/TiNi in an aqueous Bi solution (0.1 m, pH 9.2) at RT and a scan rate of 50 mV s−1 showing the increase in the NiII/III oxidation wave9a, b at approximately Ep=1.62 V versus RHE and the wave for electrocatalytic water oxidation at an onset potential of approximately Ecat=1.73 V versus RHE. A platinum counter and a Ag/AgCl/KCl(sat) reference electrode were employed. b) Amount of O2 evolved during controlled potential electrolysis with FTO/TiNi under the same conditions at an applied potential of 2.0 V versus RHE between one and seven hours. The amount of O2 was quantified by an O2 fluorescence probe (solid trace) and the dashed trace shows the theoretical amount of O2 calculated based on 100 % Faradaic efficiency.

Mentions: The precursor TiNi contains a dimeric [Ni(μ-Cl)2Ni]2+ bridged core with two attached [Ti2(OEt)9]− moieties (Figure 1 a) and was readily obtained through a solvothermal reaction of Ti(OEt)4 with NiCl2.[7] We first assessed the hydrolytic decomposition of TiNi into TiO2 and the electroactivity of NiOx. A water-oxidizing electrode (FTO/TiNi) was assembled by drop-casting TiNi in toluene (10 μL of a 5 mm solution) on a fluoride-doped tin oxide (FTO)-coated glass substrate with an exposed geometrical surface area of 0.5 cm2. Hydrolysis and polycondensation of TiNi gave a mixture of amorphous TiO2 (Figure S1 in the Supporting Information)[8] and NiOx, which was confirmed by energy-dispersive X-ray (EDX) analysis (Ti to Ni ratio of ca. 2 to 1; Table S1 in the Supporting Information) and electrochemical investigations. NiOx is a known electrocatalyst for water oxidation in borate solution,[9] and NiOx on FTO/TiNi electro-oxidizes water to O2 with approximately 90 % Faradaic efficiency in potassium borate solution (0.1 m, Bi) at pH 9.2 with a potential of 2.0 V versus the reversible-hydrogen electrode (RHE, Figure 2).


Scalable one-step assembly of an inexpensive photoelectrode for water oxidation by deposition of a Ti- and Ni-containing molecular precursor on nanostructured WO3.

Lai YH, King TC, Wright DS, Reisner E - Chemistry (2013)

a) Consecutive cyclic voltammograms with FTO/TiNi in an aqueous Bi solution (0.1 m, pH 9.2) at RT and a scan rate of 50 mV s−1 showing the increase in the NiII/III oxidation wave9a, b at approximately Ep=1.62 V versus RHE and the wave for electrocatalytic water oxidation at an onset potential of approximately Ecat=1.73 V versus RHE. A platinum counter and a Ag/AgCl/KCl(sat) reference electrode were employed. b) Amount of O2 evolved during controlled potential electrolysis with FTO/TiNi under the same conditions at an applied potential of 2.0 V versus RHE between one and seven hours. The amount of O2 was quantified by an O2 fluorescence probe (solid trace) and the dashed trace shows the theoretical amount of O2 calculated based on 100 % Faradaic efficiency.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC3814423&req=5

fig02: a) Consecutive cyclic voltammograms with FTO/TiNi in an aqueous Bi solution (0.1 m, pH 9.2) at RT and a scan rate of 50 mV s−1 showing the increase in the NiII/III oxidation wave9a, b at approximately Ep=1.62 V versus RHE and the wave for electrocatalytic water oxidation at an onset potential of approximately Ecat=1.73 V versus RHE. A platinum counter and a Ag/AgCl/KCl(sat) reference electrode were employed. b) Amount of O2 evolved during controlled potential electrolysis with FTO/TiNi under the same conditions at an applied potential of 2.0 V versus RHE between one and seven hours. The amount of O2 was quantified by an O2 fluorescence probe (solid trace) and the dashed trace shows the theoretical amount of O2 calculated based on 100 % Faradaic efficiency.
Mentions: The precursor TiNi contains a dimeric [Ni(μ-Cl)2Ni]2+ bridged core with two attached [Ti2(OEt)9]− moieties (Figure 1 a) and was readily obtained through a solvothermal reaction of Ti(OEt)4 with NiCl2.[7] We first assessed the hydrolytic decomposition of TiNi into TiO2 and the electroactivity of NiOx. A water-oxidizing electrode (FTO/TiNi) was assembled by drop-casting TiNi in toluene (10 μL of a 5 mm solution) on a fluoride-doped tin oxide (FTO)-coated glass substrate with an exposed geometrical surface area of 0.5 cm2. Hydrolysis and polycondensation of TiNi gave a mixture of amorphous TiO2 (Figure S1 in the Supporting Information)[8] and NiOx, which was confirmed by energy-dispersive X-ray (EDX) analysis (Ti to Ni ratio of ca. 2 to 1; Table S1 in the Supporting Information) and electrochemical investigations. NiOx is a known electrocatalyst for water oxidation in borate solution,[9] and NiOx on FTO/TiNi electro-oxidizes water to O2 with approximately 90 % Faradaic efficiency in potassium borate solution (0.1 m, Bi) at pH 9.2 with a potential of 2.0 V versus the reversible-hydrogen electrode (RHE, Figure 2).

Bottom Line: Photoactive in one step!A nanocomposite water-oxidation photocatalyst was assembled by a straightforward and one-step spin-coating procedure of a Ti- and Ni-containing molecule on nanostructured WO3.The photoanode oxidizes water to O2 with good activity and stability in alkaline solution, and thereby features light absorption, charge separation and water-oxidation catalysis (see scheme).

View Article: PubMed Central - PubMed

Affiliation: Christian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (UK).

No MeSH data available.


Related in: MedlinePlus