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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Surface Density-of-States Engineering of Anatase TiO<sub>2</sub> by
Small Polyols for Enhanced Visible-Light Photocurrent
Generation</title><author><name sortKey="Aubert, Remko" sort="Aubert, Remko" uniqKey="Aubert R" first="Remko" last="Aubert">Remko Aubert</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Kenens, Bart" sort="Kenens, Bart" uniqKey="Kenens B" first="Bart" last="Kenens">Bart Kenens</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Chamtouri, Maha" sort="Chamtouri, Maha" uniqKey="Chamtouri M" first="Maha" last="Chamtouri">Maha Chamtouri</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Fujita, Yasuhiko" sort="Fujita, Yasuhiko" uniqKey="Fujita Y" first="Yasuhiko" last="Fujita">Yasuhiko Fujita</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Fortuni, Beatrice" sort="Fortuni, Beatrice" uniqKey="Fortuni B" first="Beatrice" last="Fortuni">Beatrice Fortuni</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Lu, Gang" sort="Lu, Gang" uniqKey="Lu G" first="Gang" last="Lu">Gang Lu</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation><affiliation><nlm:aff id="aff2">KLOFE, SICAM,<institution>Nanjing Tech University</institution>, 30 South Puzhu Road, Nanjing 211816, Jiangsu,<country>People’s Republic of China</country></nlm:aff></affiliation></author><author><name sortKey="Hutchison, James A" sort="Hutchison, James A" uniqKey="Hutchison J" first="James A." last="Hutchison">James A. Hutchison</name><affiliation><nlm:aff id="aff3"><institution>Université de Strasbourg & CNRS UMR 7006</institution>, Strasbourg 67000,<country>France</country></nlm:aff></affiliation><affiliation><nlm:aff id="aff4">School of Chemistry and Bio21 Institute,<institution>University of Melbourne</institution>, Parkville, Victoria 3010,<country>Australia</country></nlm:aff></affiliation></author><author><name sortKey="Inose, Tomoko" sort="Inose, Tomoko" uniqKey="Inose T" first="Tomoko" last="Inose">Tomoko Inose</name><affiliation><nlm:aff id="aff5">RIES,<institution>Hokkaido University</institution>, N20W10, Kita, Sapporo 001-0020,<country>Japan</country></nlm:aff></affiliation></author><author><name sortKey="Uji I, Hiroshi" sort="Uji I, Hiroshi" uniqKey="Uji I H" first="Hiroshi" last="Uji-I">Hiroshi Uji-I</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation><affiliation><nlm:aff id="aff5">RIES,<institution>Hokkaido University</institution>, N20W10, Kita, Sapporo 001-0020,<country>Japan</country></nlm:aff></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">PMC</idno><idno type="pmid">29104949</idno><idno type="pmc">5664144</idno><idno type="url">http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5664144</idno><idno type="RBID">PMC:5664144</idno><idno type="doi">10.1021/acsomega.7b00853</idno><date when="2017">2017</date><idno type="wicri:Area/Pmc/Corpus">000688</idno><idno type="wicri:explorRef" wicri:stream="Pmc" wicri:step="Corpus" wicri:corpus="PMC">000688</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en" level="a" type="main">Surface Density-of-States Engineering of Anatase TiO<sub>2</sub> by
Small Polyols for Enhanced Visible-Light Photocurrent
Generation</title><author><name sortKey="Aubert, Remko" sort="Aubert, Remko" uniqKey="Aubert R" first="Remko" last="Aubert">Remko Aubert</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Kenens, Bart" sort="Kenens, Bart" uniqKey="Kenens B" first="Bart" last="Kenens">Bart Kenens</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Chamtouri, Maha" sort="Chamtouri, Maha" uniqKey="Chamtouri M" first="Maha" last="Chamtouri">Maha Chamtouri</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Fujita, Yasuhiko" sort="Fujita, Yasuhiko" uniqKey="Fujita Y" first="Yasuhiko" last="Fujita">Yasuhiko Fujita</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Fortuni, Beatrice" sort="Fortuni, Beatrice" uniqKey="Fortuni B" first="Beatrice" last="Fortuni">Beatrice Fortuni</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation></author><author><name sortKey="Lu, Gang" sort="Lu, Gang" uniqKey="Lu G" first="Gang" last="Lu">Gang Lu</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation><affiliation><nlm:aff id="aff2">KLOFE, SICAM,<institution>Nanjing Tech University</institution>, 30 South Puzhu Road, Nanjing 211816, Jiangsu,<country>People’s Republic of China</country></nlm:aff></affiliation></author><author><name sortKey="Hutchison, James A" sort="Hutchison, James A" uniqKey="Hutchison J" first="James A." last="Hutchison">James A. Hutchison</name><affiliation><nlm:aff id="aff3"><institution>Université de Strasbourg & CNRS UMR 7006</institution>, Strasbourg 67000,<country>France</country></nlm:aff></affiliation><affiliation><nlm:aff id="aff4">School of Chemistry and Bio21 Institute,<institution>University of Melbourne</institution>, Parkville, Victoria 3010,<country>Australia</country></nlm:aff></affiliation></author><author><name sortKey="Inose, Tomoko" sort="Inose, Tomoko" uniqKey="Inose T" first="Tomoko" last="Inose">Tomoko Inose</name><affiliation><nlm:aff id="aff5">RIES,<institution>Hokkaido University</institution>, N20W10, Kita, Sapporo 001-0020,<country>Japan</country></nlm:aff></affiliation></author><author><name sortKey="Uji I, Hiroshi" sort="Uji I, Hiroshi" uniqKey="Uji I H" first="Hiroshi" last="Uji-I">Hiroshi Uji-I</name><affiliation><nlm:aff id="aff1">Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></nlm:aff></affiliation><affiliation><nlm:aff id="aff5">RIES,<institution>Hokkaido University</institution>, N20W10, Kita, Sapporo 001-0020,<country>Japan</country></nlm:aff></affiliation></author></analytic><series><title level="j">ACS Omega</title><idno type="eISSN">2470-1343</idno><imprint><date when="2017">2017</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en"><p content-type="toc-graphic"><graphic xlink:href="ao-2017-00853e_0004" id="ab-tgr1"></graphic></p><p>Enhancement
of visible-light photocurrent generation by sol–gel
anatase TiO<sub>2</sub> films was achieved by binding small polyol
molecules to the TiO<sub>2</sub> surface. Binding ethylene glycol
onto the surface, enhancement factors up to 2.8 were found in visible-light
photocurrent generation experiments. Density functional theory calculations
identified midgap energy states that emerge as a result of the binding
of a range of polyols to the TiO<sub>2</sub> surface. The presence
and energy of the midgap state is predicted to depend sensitively
on the structure of the polyol, correlating well with the photocurrent
generation results. Together, these results suggest a new, facile,
and cost-effective route to precise surface band gap engineering of
TiO<sub>2</sub> toward visible-light-induced photocatalysis and energy
storage.</p></div></front><back><div1 type="bibliography"><listBibl><biblStruct><analytic><author><name sortKey="Crabtree, G W" uniqKey="Crabtree G">G. W. Crabtree</name></author><author><name sortKey="Lewis, N S" uniqKey="Lewis N">N. S. Lewis</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Malato, S" uniqKey="Malato S">S. Malato</name></author><author><name sortKey="Blanco, J" uniqKey="Blanco J">J. Blanco</name></author><author><name sortKey="Vidal, A" uniqKey="Vidal A">A. Vidal</name></author><author><name sortKey="Richter, C" uniqKey="Richter C">C. Richter</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Bahnemann, D" uniqKey="Bahnemann D">D. Bahnemann</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chong, M N" uniqKey="Chong M">M. N. Chong</name></author><author><name sortKey="Jin, B" uniqKey="Jin B">B. Jin</name></author><author><name sortKey="Chow, C W K" uniqKey="Chow C">C. W. K. Chow</name></author><author><name sortKey="Saint, C" uniqKey="Saint C">C. Saint</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Fujishima, A" uniqKey="Fujishima A">A. Fujishima</name></author><author><name sortKey="Tryk, D X0a A" uniqKey="Tryk D">D.
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<front><journal-meta><journal-id journal-id-type="nlm-ta">ACS Omega</journal-id><journal-id journal-id-type="iso-abbrev">ACS Omega</journal-id><journal-id journal-id-type="publisher-id">ao</journal-id><journal-id journal-id-type="coden">acsodf</journal-id><journal-title-group><journal-title>ACS Omega</journal-title></journal-title-group><issn pub-type="epub">2470-1343</issn><publisher><publisher-name>American Chemical Society</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="pmid">29104949</article-id><article-id pub-id-type="pmc">5664144</article-id><article-id pub-id-type="doi">10.1021/acsomega.7b00853</article-id><article-categories><subj-group><subject>Article</subject></subj-group></article-categories><title-group><article-title>Surface Density-of-States Engineering of Anatase TiO<sub>2</sub> by
Small Polyols for Enhanced Visible-Light Photocurrent
Generation</article-title></title-group><contrib-group><contrib contrib-type="author" id="ath1"><name><surname>Aubert</surname><given-names>Remko</given-names></name><xref rid="aff1" ref-type="aff">†</xref></contrib><contrib contrib-type="author" id="ath2"><name><surname>Kenens</surname><given-names>Bart</given-names></name><xref rid="aff1" ref-type="aff">†</xref></contrib><contrib contrib-type="author" id="ath3"><name><surname>Chamtouri</surname><given-names>Maha</given-names></name><xref rid="aff1" ref-type="aff">†</xref></contrib><contrib contrib-type="author" id="ath4"><name><surname>Fujita</surname><given-names>Yasuhiko</given-names></name><xref rid="aff1" ref-type="aff">†</xref></contrib><contrib contrib-type="author" id="ath5"><name><surname>Fortuni</surname><given-names>Beatrice</given-names></name><xref rid="aff1" ref-type="aff">†</xref></contrib><contrib contrib-type="author" id="ath6"><name><surname>Lu</surname><given-names>Gang</given-names></name><xref rid="aff1" ref-type="aff">†</xref><xref rid="aff2" ref-type="aff">‡</xref></contrib><contrib contrib-type="author" id="ath7"><name><surname>Hutchison</surname><given-names>James A.</given-names></name><xref rid="aff3" ref-type="aff">§</xref><xref rid="aff4" ref-type="aff">∥</xref></contrib><contrib contrib-type="author" id="ath8"><name><surname>Inose</surname><given-names>Tomoko</given-names></name><xref rid="aff5" ref-type="aff">⊥</xref></contrib><contrib contrib-type="author" corresp="yes" id="ath9"><name><surname>Uji-i</surname><given-names>Hiroshi</given-names></name><xref rid="cor1" ref-type="other">*</xref><xref rid="aff1" ref-type="aff">†</xref><xref rid="aff5" ref-type="aff">⊥</xref></contrib><aff id="aff1"><label>†</label>Department of Chemistry,<institution>KU Leuven</institution>, Celestijnenlaan 200F, B-3001 Heverlee,<country>Belgium</country></aff><aff id="aff2"><label>‡</label>KLOFE, SICAM,<institution>Nanjing Tech University</institution>, 30 South Puzhu Road, Nanjing 211816, Jiangsu,<country>People’s Republic of China</country></aff><aff id="aff3"><label>§</label><institution>Université de Strasbourg & CNRS UMR 7006</institution>, Strasbourg 67000,<country>France</country></aff><aff id="aff4"><label>∥</label>School of Chemistry and Bio21 Institute,<institution>University of Melbourne</institution>, Parkville, Victoria 3010,<country>Australia</country></aff><aff id="aff5"><label>⊥</label>RIES,<institution>Hokkaido University</institution>, N20W10, Kita, Sapporo 001-0020,<country>Japan</country></aff></contrib-group><author-notes><corresp id="cor1"><label>*</label>E-mail: <email>hiroshi.ujii@kuleuven.be</email>, <email>hiroshi.ujii@es.hokudai.ac.jp</email>.</corresp></author-notes><pub-date pub-type="epub"><day>02</day><month>10</month><year>2017</year></pub-date><pub-date pub-type="ppub"><day>31</day><month>10</month><year>2017</year></pub-date><volume>2</volume><issue>10</issue><fpage>6309</fpage><lpage>6313</lpage><history><date date-type="received"><day>23</day><month>06</month><year>2017</year></date><date date-type="accepted"><day>16</day><month>08</month><year>2017</year></date></history><permissions><copyright-statement>Copyright © 2017 American Chemical Society</copyright-statement><copyright-year>2017</copyright-year><copyright-holder>American Chemical Society</copyright-holder><license><license-p>This is an open access article published under an ACS AuthorChoice <ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/page/policy/authorchoice_termsofuse.html">License</ext-link>, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.</license-p></license></permissions><abstract><p content-type="toc-graphic"><graphic xlink:href="ao-2017-00853e_0004" id="ab-tgr1"></graphic></p><p>Enhancement
of visible-light photocurrent generation by sol–gel
anatase TiO<sub>2</sub> films was achieved by binding small polyol
molecules to the TiO<sub>2</sub> surface. Binding ethylene glycol
onto the surface, enhancement factors up to 2.8 were found in visible-light
photocurrent generation experiments. Density functional theory calculations
identified midgap energy states that emerge as a result of the binding
of a range of polyols to the TiO<sub>2</sub> surface. The presence
and energy of the midgap state is predicted to depend sensitively
on the structure of the polyol, correlating well with the photocurrent
generation results. Together, these results suggest a new, facile,
and cost-effective route to precise surface band gap engineering of
TiO<sub>2</sub> toward visible-light-induced photocatalysis and energy
storage.</p></abstract><custom-meta-group><custom-meta><meta-name>document-id-old-9</meta-name><meta-value>ao7b00853</meta-value></custom-meta><custom-meta><meta-name>document-id-new-14</meta-name><meta-value>ao-2017-00853e</meta-value></custom-meta><custom-meta><meta-name>ccc-price</meta-name><meta-value></meta-value></custom-meta></custom-meta-group></article-meta></front><body><sec id="sec1"><title>Introduction</title><p>An increasing number
of important processes are now being transitioned
to using sunlight as their energy source,<sup><xref ref-type="bibr" rid="ref1">1</xref>,<xref ref-type="bibr" rid="ref2">2</xref></sup> including
pollutant degradation,<sup><xref ref-type="bibr" rid="ref3">3</xref>−<xref ref-type="bibr" rid="ref7">7</xref></sup> photocurrent generation,<sup><xref ref-type="bibr" rid="ref8">8</xref>−<xref ref-type="bibr" rid="ref11">11</xref></sup> and high energy content chemical synthesis.<sup><xref ref-type="bibr" rid="ref12">12</xref>−<xref ref-type="bibr" rid="ref16">16</xref></sup> In designing devices for these applications, a fine balance must
be struck between the energy-conversion efficiency of the device,
the lifetime of the end product, and other factors, such as material
cost/abundance, toxicity, and physicochemical stability.<sup><xref ref-type="bibr" rid="ref17">17</xref></sup> Because of its good performance in the latter
categories, titanium dioxide (TiO<sub>2</sub>) is commonly used as
a photoactive material in devices.<sup><xref ref-type="bibr" rid="ref18">18</xref>−<xref ref-type="bibr" rid="ref20">20</xref></sup> Furthermore, the energy
levels of the valence and conduction bands (CBs) of TiO<sub>2</sub> envelop the oxidation and reduction energies of H<sub>2</sub>O,
respectively, making it especially suitable for water-splitting applications.<sup><xref ref-type="bibr" rid="ref12">12</xref>,<xref ref-type="bibr" rid="ref14">14</xref>,<xref ref-type="bibr" rid="ref15">15</xref></sup></p><p>One of the biggest drawbacks
in the TiO<sub>2</sub> applications
is its wide band gap (∼3.2 eV for the most active crystal form,
anatase TiO<sub>2</sub>). This limits the spectral range of absorbable
solar photons to the UV region (λ < 400 nm); only about 5%
of the light reaches the earth’s surface.<sup><xref ref-type="bibr" rid="ref17">17</xref>,<xref ref-type="bibr" rid="ref21">21</xref></sup> Much effort has been expended to increase the visible-light activity
of TiO<sub>2</sub>, including elementary doping,<sup><xref ref-type="bibr" rid="ref22">22</xref>−<xref ref-type="bibr" rid="ref25">25</xref></sup> dye sensitization,<sup><xref ref-type="bibr" rid="ref26">26</xref>−<xref ref-type="bibr" rid="ref28">28</xref></sup> plasmonic enhancement,<sup><xref ref-type="bibr" rid="ref15">15</xref>,<xref ref-type="bibr" rid="ref29">29</xref></sup> and surface modification
by organic molecules.<sup><xref ref-type="bibr" rid="ref30">30</xref>−<xref ref-type="bibr" rid="ref32">32</xref></sup> Although visible-light activity was achieved in these
approaches, sacrifices were also made in terms of material performance.
For example, although elementary doping engineers the band gap in
a way that enables visible photoactivity, it usually also reduces
the physicochemical stability of TiO<sub>2</sub>. In the case of surface
modification with organic molecules and dye sensitization, most of
the progress was made using aromatic compounds as charge-transfer
agents.<sup><xref ref-type="bibr" rid="ref32">32</xref>,<xref ref-type="bibr" rid="ref33">33</xref></sup> These compounds are generally not very soluble
in water, limiting their application potential, and their degradation
during photocatalytic processes is a constant issue. A more serious
drawback when using aromatic charge-transfer agents is that they are
often toxic and can negatively impact the environment.</p><p>In this
work, we present a solution to the latter problem, demonstrating
that visible-light activity of TiO<sub>2</sub> can be enhanced by
adding simple, relatively nontoxic, water soluble organic surface-binding
agents, small polyols. Despite the lack of charge-transfer moieties
and/or absorption bands in the visible region in these polyols, an
increase in TiO<sub>2</sub> visible-light activity by up to 2.8 times
is observed in their presence in photocurrent generation experiments.
The mechanism of enhancement is revealed by density functional theory
(DFT) calculations, which show that polyol binding to TiO<sub>2</sub> results in generation of mid-band-gap energy states that can interact
with visible photons. The energy of these mid-band-gap states is found
to depend on the polyol structure, allowing surface DOS engineering
and optimization of TiO<sub>2</sub> visible photoactivity in a facile
and cost-effective manner.</p></sec><sec id="sec2"><title>Results and Discussion</title><p>The effect
of the molecular adsorption on the photoactivity of
sol–gel derived anatase TiO<sub>2</sub> films on fluorine tin
oxide (FTO) in visible light was found in photocurrent generation
experiments, an analysis tool successfully employed in similar studies
on semiconductor photoactivity.<sup><xref ref-type="bibr" rid="ref34">34</xref>,<xref ref-type="bibr" rid="ref35">35</xref></sup> The photocurrent was
measured using an electrochemical analyzer and a three-electrode cell
consisting of the TiO<sub>2</sub> film as the working electrode (W.E.),
a Pt wire counter electrode (C.E.), and an AgCl/Ag reference electrode
(R.E.), all immersed in a 0.1 M KOH aqueous electrolyte bath (<xref rid="fig1" ref-type="fig">Figure <xref rid="fig1" ref-type="fig">1</xref></xref>). The cell was designed
such that a 150 W solar simulator lamp could irradiate the TiO<sub>2</sub> film with a 430 nm long-pass filter available to isolate
the contribution of visible light (λ > 430 nm, <ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S1</ext-link>).</p><fig id="fig1" position="float"><label>Figure 1</label><caption><p>Schematic representation of the used setup
in photocurrent generation
experiments.</p></caption><graphic xlink:href="ao-2017-00853e_0006" id="gr2" position="float"></graphic></fig><p>The effect of the molecular
adsorption on the photoactivity of
sol–gel derived anatase TiO<sub>2</sub> films on fluorine tin
oxide (FTO) in visible light was found in photocurrent generation
experiments. To investigate the effect of polyol molecules on photocatalytic
activity in visible light, the activity was compared before and after
addition of polyol molecules to the electrolyte. During a measurement,
the lamp light was alternatively blocked or allowed to impinge on
the TiO<sub>2</sub> film, for alternating 30 s periods, creating a
block-wave pattern in the measured photocurrent (<xref rid="fig2" ref-type="fig">Figure <xref rid="fig2" ref-type="fig">2</xref></xref>a). The initial photoactivity
was determined using three on–off cycles of 60 s and averaging
the step heights between the light and dark periods. Subsequently,
the polyol was added as indicated with the arrow in <xref rid="fig2" ref-type="fig">Figure <xref rid="fig2" ref-type="fig">2</xref></xref>a so that the change in the
photocatalytic activity of the same sol–gel film can be compared.
The final concentration of the polyol in the electrolyte is set to
be ∼1.8 M. The newly created system was allowed to mix for
120 s, and then the activity was resolved using another three cycles.
Note that although about 200 times smaller compared with activity
in full solar spectral (full) light, including UV light (<ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S1</ext-link>), our TiO<sub>2</sub> films are slightly
visible-active even before addition of molecules. This could be due
to oxygen vacancies on the surface that have emerged during preparation
or calcination.<sup><xref ref-type="bibr" rid="ref23">23</xref>,<xref ref-type="bibr" rid="ref36">36</xref></sup> This activity, however, is crucial
for the quantitative analysis of the effect of the added polyols because
the enhancement factor (EF) in this study is given by the ratio between
the photocurrent before and after polyol addition to the same sol–gel
TiO<sub>2</sub> film.</p><fig id="fig2" position="float"><label>Figure 2</label><caption><p>(a) Typical photocurrent generation experiments before
and after
adding polyols in the electrolyte. The result with glycerol is shown
as an example. (b) Photocurrents found before (red) and after (blue)
addition of the specific molecule in the electrolyte. (c) Enhancement
factors of each molecule derived from the values in (b).</p></caption><graphic xlink:href="ao-2017-00853e_0001" id="gr3" position="float"></graphic></fig><p>To understand this effect, we have studied several
polyol molecules,
as shown in <xref rid="sch1" ref-type="scheme">Scheme <xref rid="sch1" ref-type="scheme">1</xref></xref>. Among them, we first investigated the effect of the number of −OH
groups and thus the hole-scavenging effect of ethanol (EtOH), ethylene
glycol (EG), and glycerol (GC). Higher enhancement can be predicted
when having more OH groups due to increase of the hole-scavenging
power, expected to be in the order of EtOH < EG < GC. The photocurrent
activities for these molecules and H<sub>2</sub>O as control are displayed
in <xref rid="fig2" ref-type="fig">Figure <xref rid="fig2" ref-type="fig">2</xref></xref>b. As can
be seen in the figure, every sol–gel film shows different photocurrent
activity even before polyol addition due to the heterogeneous feature
of the sol–gel film. As mentioned before, for the quantitative
analysis, the ratios between activities before (red bars) and after
(blue bars) polyol addition are given as the enhancement factor (EF)
for each molecule in visible light (<xref rid="fig2" ref-type="fig">Figure <xref rid="fig2" ref-type="fig">2</xref></xref>c). It is clear that visible activity is
enhanced upon addition of all used molecules. Addition of EG shows
the highest EFs (>2.8), whereas EtOH and GC show similar EFs, less
than 2. This result suggests that the number of −OH groups
is not responsible only for the enhancement.</p><fig id="sch1" position="float"><label>Scheme 1</label><caption><title>Chemical Structures
of the Investigated Molecules</title></caption><graphic xlink:href="ao-2017-00853e_0005" id="gr1" position="float"></graphic></fig><p>To investigate the influence of the molecules on the visible
photocatalytic
activity more precisely, the experiment was conducted using TiO<sub>2</sub> films that were pretreated with polyol molecules; namely,
the sol–gel film was immersed in each polyol for 68 h and subsequently
rinsed with water and isopropanol several times and dried with Ar
gas. These pretreated sol–gel films were subjected to the photocurrent
experiment using pure 1 M KOH electrolyte without adding polyols to
the electrolyte. In such a way, we can discuss only the effect of
adsorbed polyol molecules on the TiO<sub>2</sub> surface and can avoid
the unexpected effect of the polyols in the electrolyte, such as the
continuous hole-scavenging effect by the molecular adsorption and
desorption dynamics.</p><p>In this pretreatment study, the series
of polyol molecules was
expanded with propylene glycol (PG) and 1,3-propanediol (PD) (<xref rid="sch1" ref-type="scheme">Scheme <xref rid="sch1" ref-type="scheme">1</xref></xref>). PD has one extra
carbon compared with EG, which could affect adsorption of polyols
on the TiO<sub>2</sub> surface. PG is very similar to EG and thus
could similarly adsorb on the surface as EG but it is a stronger electron
donor than EG. <xref rid="fig3" ref-type="fig">Figure <xref rid="fig3" ref-type="fig">3</xref></xref> shows that the photocurrent EF obtained on TiO<sub>2</sub> sol–gel
films is pretreated with H<sub>2</sub>O, EtOH, EG, PG, PD, and GC.
Note that the sol–gel film treated with H<sub>2</sub>O was
used as the control. In this pretreatment experiment, after the photocurrent
experiments with visible light, the sample was irradiated with UV
light until all of the adsorbed molecules decomposed. Then EF was
calculated using the value of the photocurrent on the freshly treated
film and that from the UV-irradiated film. In such a way, quantitative
estimation of EF was realized on the same sol–gel film. As
shown in <xref rid="fig3" ref-type="fig">Figure <xref rid="fig3" ref-type="fig">3</xref></xref>,
the films treated with EtOH and polyols exhibit higher EF compared
to the control, indicating these molecules strongly adsorb and remain
on the surface of TiO<sub>2</sub> even after the several rinsing processes
and affect on the photocurrent activity. The EFs for these molecules
are found in the order of EG > PG > GC > PD > EtOH >
H<sub>2</sub>O.</p><fig id="fig3" position="float"><label>Figure 3</label><caption><p>Enhancement factors of photocurrent generation obtained
with TiO<sub>2</sub> sol–gel films pretreated without and with
EtOH, EG,
PG, PD, and GC.</p></caption><graphic xlink:href="ao-2017-00853e_0002" id="gr4" position="float"></graphic></fig><p>Further, the very similar
EF values found in the pretreatment experiment
(<xref rid="fig3" ref-type="fig">Figure <xref rid="fig3" ref-type="fig">3</xref></xref>) and those
in the addition experiment (<xref rid="fig2" ref-type="fig">Figure <xref rid="fig2" ref-type="fig">2</xref></xref>c) suggest that the polyol–TiO<sub>2</sub> interaction,
once established, is of similar nature in both cases.</p><p>To investigate
this interaction in more depth, we have tried to
obtain additional evidence for molecular functionalization and the
type of adsorption of the molecules to the surface using Fourier transform
infrared (FTIR) spectroscopy and Raman spectroscopy. The restricted
sensitivity of these spectroscopic tools combined with the limited
layer thickness of the functionalized layer, however, made it too
hard to obtain the extra evidence in this way.</p><p>Polyols adsorbed
on semiconductor surfaces have been studied in
the past. In 2004, a number of articles were published regarding hole-scavenging
by polyol molecules on TiO<sub>2</sub> surfaces.<sup><xref ref-type="bibr" rid="ref37">37</xref>,<xref ref-type="bibr" rid="ref38">38</xref></sup> It is known that hole-scavenging decreases the recombination rate
of the generated excitons and thus improves the photocatalytic activity.
More recently, increased photocatalytic activity in UV light was shown
for Au/TiO<sub>2</sub> systems in the presence of several polyols,
where increased photocatalytic activities were recorded with hole-scavenging
being the likely explanation.<sup><xref ref-type="bibr" rid="ref39">39</xref></sup> Interestingly,
in both experiments on the hole-scavenging efficiency by polyols (found
to increase with the number of hydroxyl groups per molecule)<sup><xref ref-type="bibr" rid="ref38">38</xref></sup> and catalytic performance studies of TiO<sub>2</sub> in the presence of polyols,<sup><xref ref-type="bibr" rid="ref41">41</xref></sup> the
order of enhancement factors was found to be GC > EG > EtOH
> H<sub>2</sub>O under UV irradiation. Further, on the basis of
their similar
hole-scavenging efficiencies, PD and EG should show comparable EFs.<sup><xref ref-type="bibr" rid="ref38">38</xref></sup> Our results obtained only with visible light
(>430 nm), however, are not consistent with these trends.</p><p>To understand the trend found in this study, we calculated the
surface local density of state (DOS) of anatase TiO<sub>2</sub> with
and without molecule adsorption. Recently, we have predicted that
EG adsorption onto the TiO<sub>2</sub> surface can give rise to midgap
energy states in its surface density of state (DOS).<sup><xref ref-type="bibr" rid="ref40">40</xref></sup> Such midgap energy states can facilitate electron excitations
into the conduction band (CB) of TiO<sub>2</sub> by light with lower
energy and thus improve the photoactivity in visible light. Here,
we present an expansion of the DFT calculations with the investigated
molecules in this report. The DFT calculation has been conducted within
the generalized gradient approximation (GGA) using the Perdew–Burke–Ernzerhof
(PBE) functional<sup><xref ref-type="bibr" rid="ref39">39</xref></sup> in the SIESTA computational
code.<sup><xref ref-type="bibr" rid="ref40">40</xref></sup> A double-ζ basis set of localized
atomic orbitals and Troullier–Martins pseudopotentials were
used for the valence and core electrons, respectively.<sup><xref ref-type="bibr" rid="ref41">41</xref></sup> Two layers of the TiO<sub>2</sub> slab is used to model the adsorption
of molecules, as depicted in <xref rid="sch1" ref-type="scheme">Scheme <xref rid="sch1" ref-type="scheme">1</xref></xref> on the {001} and {101} facets. All of the structures
were relaxed until less than 0.05 eV/Å. A Monkhorst–Pack
grid was used for the density-of-state (DOS) calculations.</p><p><xref rid="fig4" ref-type="fig">Figure <xref rid="fig4" ref-type="fig">4</xref></xref> shows the
surface DOS of TiO<sub>2</sub> with adsorption of H<sub>2</sub>O,
EtOH, EG, PG, PD, and GC, where only the results for a {001} facet
are shown because the more thermally stable yet less photoactive {101}
facet yields no midgap states likely due to the inability of the molecules
to attach dissociatively to the surface.<sup><xref ref-type="bibr" rid="ref19">19</xref>,<xref ref-type="bibr" rid="ref44">44</xref></sup> As shown in <xref rid="fig4" ref-type="fig">Figure <xref rid="fig4" ref-type="fig">4</xref></xref>, an extra energy state is found for EG, GC, and PG but not for EtOH,
H<sub>2</sub>O, and PD (<xref rid="fig4" ref-type="fig">Figure <xref rid="fig4" ref-type="fig">4</xref></xref>). Moreover, the position of the localized midgap state induced
by EG is ∼2 eV below the CB, whereas the positions for PG and
GC are ∼2.5 eV below it. The presence of these midgap states
could associate with efficient electron excitation under visible light
besides the hole-scavenging effect. Indeed, the maximum EF was found
with EG, whereas PG and GC show the second highest EF among the molecules.
The enhancement observed for EtOH and PD is smaller than that of EG,
PG, and GC and yet higher than that of H<sub>2</sub>O, which is most
likely due to the hole-scavenging effect. Therefore, taking into account
both the extra midgap state and hole-scavenging effect, EFs found
in the order of EG > PG > GC > PD > EtOH > H<sub>2</sub>O nicely correlate
with our calculation.</p><fig id="fig4" position="float"><label>Figure 4</label><caption><p>DFT-calculated density-of-states (DOSs) plot for the investigated
molecules (H<sub>2</sub>O, EtOH, EG, PG, PD, and GC) dissociatively
adsorbed on a {001} TiO<sub>2</sub> facet. The right end of the figure
shows the position of the newly created midgap states in the electronic
structure of the TiO<sub>2</sub> surface.</p></caption><graphic xlink:href="ao-2017-00853e_0003" id="gr5" position="float"></graphic></fig><p>The absence of this correlation in other studies on polyol-enhanced
TiO<sub>2</sub> photocatalysis can be attributed to the light source
employed. Other studies used UV light or sunlight including UV light,
whereas the present study used only visible light (430 < λ
< 750 nm). Because of the high photoresponse of TiO<sub>2</sub> in UV light, the response of the system to those wavelengths could
conceal the effect of the midgap states. Because we use only visible
light (λ > 430 nm) in our irradiation experiments (<ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S1</ext-link>), the effect of the midgap states is
more pronounced in the photocurrent generation experiments. The differences
in enhancement when using either wavelength range is demonstrated
in <ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S2</ext-link> for the sol–gel TiO<sub>2</sub> surfaces treated with EG.</p><p>Supported by infrared (IR)
spectroscopy<sup><xref ref-type="bibr" rid="ref45">45</xref></sup> and X-ray absorption near
edge structure (XANES) spectroscopy measurements,<sup><xref ref-type="bibr" rid="ref38">38</xref></sup> a possible interaction of polyol molecules with
defect sites on the TiO<sub>2</sub> surface was suggested previously,
involving an octahedrally coordinated Ti-atom chelated by two hydroxyl
groups of the polyol. In other studies, the interaction between hydroxyl
groups and TiO<sub>2</sub> was used to anchor larger molecules to
the semiconductor surface.<sup><xref ref-type="bibr" rid="ref32">32</xref>,<xref ref-type="bibr" rid="ref33">33</xref></sup> From our results, we
conclude that the interaction of polyols with the surface is of great
importance to surface DOS engineering. According to our calculation,
all molecules showing midgap energy states also feature a noncoordinating
hydroxyl group (<ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S4B–D</ext-link>). When
the number of backbone carbon atoms is increased above two, two different
Ti atoms can be bound by the hydroxyl groups on either end of the
molecule, converting the free hydroxyl group into a binding oxygen
atom (<ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S4E</ext-link>). The presence of a free
hydroxyl group for EG, PG, and GC but not for PD and the presence
and absence, respectively, of a midgap energy state, as predicted
by DFT, further supports this scenario.</p></sec><sec id="sec3"><title>Conclusions</title><p>In
conclusion, the photocatalytic performance of TiO<sub>2</sub> films
in visible light was improved by applying several small polyols
to the surface. For a select number of polyols with similarities in
the carbon backbone, the performance increase was found to be higher
due to the appearance of an extra mid-band-gap energy state. With
these results, the efficiency of photocatalysis, energy storage, or
direct energy production using solar light can be further increased,
supporting a worldwide transition from conventional to sustainable
energy sources.</p></sec><sec id="sec4"><title>Experimental Section</title><p>Anatase TiO<sub>2</sub> films on FTO were prepared using a sol–gel
method, with Ti(OPr)<sub>4</sub> as the precursor salt and the annealing
temperature of 475 °C.<sup><xref ref-type="bibr" rid="ref46">46</xref></sup> Full saturation
of the TiO<sub>2</sub> surface with polyol molecules was achieved
by either immersing the samples in the pure compound for 68 h or by
adding the pure compound to the electrolyte medium during photocurrent
generation experiments, as will be discussed further below.</p><p>In a typical experiment, the photocurrent was measured using an
electrochemical analyzer and a three-electrode cell consisting of
the TiO<sub>2</sub> film as the working electrode (W.E.), a Pt wire
counter electrode (C.E.), and an AgCl/Ag reference electrode (R.E.),
all immersed in a 0.1 M KOH aqueous electrolyte bath (<xref rid="fig1" ref-type="fig">Figure <xref rid="fig1" ref-type="fig">1</xref></xref>). The cell was designed such
that a 150 W solar simulator lamp could irradiate the TiO<sub>2</sub> film with a 430 nm long-pass filter available to isolate the contribution
of visible light (OD > 5 below 430 nm, <ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">Figure S5</ext-link>). The Ohmic contact between the TiO<sub>2</sub> film and
the wiring was improved using Cu tape and an In/Ga paste.</p><p>All
of the polyols employed here as well as the Ti(OPr)<sub>4</sub> were
purchased from Sigma-Aldrich, with a purity of at least 98%,
and used without further purification. Both the electrochemical analyzer
and the AgCl/Ag reference electrode were purchased at CH instruments.
The solar simulator, model number 67005, was provided by Newport,
Oriental Intruments. The 430 nm long-pass filter, HQ430LP, was purchased
at Chroma.</p><p>We used density functional theory (DFT) calculations
within the
generalized gradient approximation (GGA) within the Perdew–Burke–Ernzerhof
(PBE) form,<sup><xref ref-type="bibr" rid="ref41">41</xref></sup> as implemented in the SIESTA
code.<sup><xref ref-type="bibr" rid="ref42">42</xref></sup> The core electrons were replaced
by Troullier–Martins pseudopotentials.<sup><xref ref-type="bibr" rid="ref43">43</xref></sup> A double-ζ basis set of localized atomic orbitals was used
for the valence electrons. A mesh cutoff energy of 300 Ry has been
imposed for real-space integration. All structures have been relaxed
until forces were less than 0.05 eV/Å. In the calculations, a
vacuum interval of more than 15 Å was used to avoid the interaction
between the periodic slabs. The surface area of anatase TiO<sub>2</sub> {001} used in the calculations is 7.57 Å × 7.57 Å.
When relaxing the atomic structures, the sampling of the Brillouin
zone was restricted to the Γ point and a (10 × 10 ×
1) Monkhorst–Pack grid was used later on for DOS calculations.<sup><xref ref-type="bibr" rid="ref47">47</xref>,<xref ref-type="bibr" rid="ref48">48</xref></sup></p></sec></body><back><notes id="notes-1" notes-type="si"><title>Supporting Information Available</title><p>The
Supporting Information
is available free of charge on the <ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org">ACS Publications website</ext-link> at DOI: <ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/abs/10.1021/acsomega.7b00853">10.1021/acsomega.7b00853</ext-link>.<list id="silist" list-type="simple"><list-item><p>Brief description
photocurrent experiments and supporting
figures (<ext-link ext-link-type="uri" xlink:href="http://pubs.acs.org/doi/suppl/10.1021/acsomega.7b00853/suppl_file/ao7b00853_si_001.pdf">PDF</ext-link>)</p></list-item></list></p></notes><sec sec-type="supplementary-material"><title>Supplementary Material</title><supplementary-material content-type="local-data" id="sifile1"><media xlink:href="ao7b00853_si_001.pdf"><caption><p>ao7b00853_si_001.pdf</p></caption></media></supplementary-material></sec><notes id="notes-2"><title>Author Contributions</title><p>The
manuscript
was written through contributions of all authors. All authors have
given approval to the final version of the manuscript.</p></notes><notes id="notes-3" notes-type="COI-statement"><p>The authors
declare no competing financial interest.</p></notes><ack><title>Acknowledgments</title><p>This work
was supported by the JST PRESTO program and the
European Research Council (ERC) grant (PLASMHACAT #280064). Support
from the Research Foundation, Flanders (FWO) (G0B5514N, G081916N,
G056314N, and G025912N) and KU Leuven Research Fund (GOA 2011/03,
OT/12/059, IDO/12/008, and C14/15/053) and funding from the Belgian
Federal Science Policy Office (IAP-VI/27) and JSPS KAKENHI (JP17H03003,
JP17H05244, and JP17H05458) are gratefully acknowledged. G.L. acknowledges
FWO for postdoctoral fellowships.</p></ack><ref-list><title>References</title><ref id="ref1"><mixed-citation publication-type="journal" id="cit1"><name><surname>Crabtree</surname><given-names>G. W.</given-names></name>; <name><surname>Lewis</surname><given-names>N. S.</given-names></name><source>Phys. Today</source><year>2007</year>, <volume>60</volume>, <fpage>37</fpage>–<lpage>42</lpage><pub-id pub-id-type="doi">10.1063/1.2718755</pub-id>.</mixed-citation></ref><ref id="ref2"><mixed-citation publication-type="journal" id="cit2"><name><surname>Malato</surname><given-names>S.</given-names></name>; <name><surname>Blanco</surname><given-names>J.</given-names></name>; <name><surname>Vidal</surname><given-names>A.</given-names></name>; <name><surname>Richter</surname><given-names>C.</given-names></name><source>Appl. Catal., B</source><year>2002</year>, <volume>37</volume>, <fpage>1</fpage>–<lpage>15</lpage><pub-id pub-id-type="doi">10.1016/S0926-3373(01)00315-0</pub-id>.</mixed-citation></ref><ref id="ref3"><mixed-citation publication-type="journal" id="cit3"><name><surname>Bahnemann</surname><given-names>D.</given-names></name><source>Sol. Energy</source><year>2004</year>, <volume>77</volume>, <fpage>445</fpage>–<lpage>459</lpage><pub-id pub-id-type="doi">10.1016/j.solener.2004.03.031</pub-id>.</mixed-citation></ref><ref id="ref4"><mixed-citation publication-type="journal" id="cit4"><name><surname>Chong</surname><given-names>M. N.</given-names></name>; <name><surname>Jin</surname><given-names>B.</given-names></name>; <name><surname>Chow</surname><given-names>C. W. K.</given-names></name>; <name><surname>Saint</surname><given-names>C.</given-names></name><source>Water Res.</source><year>2010</year>, <volume>44</volume>, <fpage>2997</fpage>–<lpage>3027</lpage><pub-id pub-id-type="doi">10.1016/j.watres.2010.02.039</pub-id>.<pub-id pub-id-type="pmid">20378145</pub-id></mixed-citation></ref><ref id="ref5"><mixed-citation publication-type="book" id="cit5"><person-group person-group-type="allauthors"><name><surname>Fujishima</surname><given-names>A.</given-names></name>; <name><surname>Tryk</surname><given-names>D.
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