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Article
High-Resolution Analysis of Photoanodes for Water Splitting
by Means of Scanning Photoelectrochemical Microscopy
Felipe Conzuelo, Kirill Sliozberg, Ramona Gutkowski,
Stefanie Grützke, Michaela Nebel, and Wolfgang Schuhmann
Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.6b03706 • Publication Date (Web): 19 Dec 2016
Downloaded from http://pubs.acs.org on December 20, 2016

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Page 1 of 9 Analytical Chemistry

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7 High-Resolution Analysis of Photoanodes for Water Splitting by
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Means of Scanning Photoelectrochemical Microscopy
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Felipe Conzuelo,a Kirill Sliozberg,a Ramona Gutkowski,a Stefanie Grützke,a Michaela Nebel,b
12 Wolfgang Schuhmanna,*
13 a
Analytical Chemistry – Center for Electrochemical Sciences (CES), Ruhr-Universität Bochum, Universitätsstr. 150,
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D-44780 Bochum, Germany
15 b
16 Sensolytics GmbH, Universitätsstr. 142, D-44799 Bochum, Germany
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18 * Corresponding Author E-Mail: wolfgang.schuhmann@rub.de, Fax: +49 234 3214683
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21 ABSTRACT: In pursuance of efficient tools for the local analysis and characterization of novel photoelectrocatalytic materials,
22 several SECM-based techniques have been developed, aiming on the combined benefit of a local irradiation of the analyzed sample
23 and a microelectrode probe for the localized electrochemical analysis of the surface. We present the development and application of
24 scanning photoelectrochemical microscopy (SPECM) for the laterally resolved characterization of photoelectrocatalytic materials.
25 Particularly, the system was developed for the photoelectrochemical characterization of n-type semiconductor-based photoanodes
26 for water splitting. By using the tip microelectrode simultaneously for local irradiation and as an electrochemical probe, SPECM
27 was capable to simultaneously providing information about the local photocurrent generated at the sample under irradiation and to
detect the photoelectrocatalytically evolved oxygen at the microelectrode. In combination with a novel means of irradiation of the
28
interrogated sample local analysis of semiconductor materials for light-induced water splitting with improved lateral resolution is
29 achieved.
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31
conversion devices with improved efficiency. In this regard,
32 KEYWORDS: scanning electrochemical microscopy; scan-
scanning electrochemical microscopy (SECM) has proven to
33 ning photoelectrochemical microscopy; SECM; SPECM;
be a powerful tool for the analysis of a wide variety of surfac-
34 in-situ oxygen detection; photoelectrocatalysis; BiVO 4
es and has been applied to the study and screening of different
35 INTRODUCTION photocatalysts.4,6-8 SECM is a scanning probe technique used
36 for the study of local electrochemical properties of a surface.9
37 In search for renewable clean energies the development of In addition, SECM was applied as a rapid method for the
38 more efficient energy conversion devices is of great im- evaluation of libraries of photocatalysts10 and is supposed to
39 portance. Of particular attention is the light-driven electrolysis be capable of providing in-depth characterization of photoac-
40 of water, where sunlight acts as source of energy allowing the tive systems.
formation of H2 under simultaneous evolution of O2.1-3 With The interrogation of photoactive materials under dark and
41
the aim to obtaining highly efficient devices for water split- controlled irradiation conditions is of great importance. Sever-
42 ting, catalysts are required which are able to decrease the
43 al studies have addressed the analysis of photoactive samples
overpotential necessary for the hydrogen evolution reaction using SECM. At first, interrogation and characterization of
44 (HER) and the oxygen evolution reaction (OER). Particularly,
45 semiconductor materials was performed using a conventional
photoelectrochemical systems based on semiconductor materi- SECM set-up, working under global irradiation of the ana-
46 als have shown high efficiencies for the conversion of solar lyzed sample.8,11-15 However, under irradiation of the entire
47 energy to fuels or electricity. While the HER is a comparative- sample the recorded photocurrent is generated at the entire
48 ly easily catalyzed process featuring a low overpotential, the sample surface. Hence, local changes of photoelectrocatalytic
49 OER requires a significant overpotential even with the best activity cannot be derived therefore impeding the characteriza-
50 known electrocatalysts due to the four-electron/four-proton tion of complex samples such as materials libraries. Moreover,
51 transfer process.4 Metals and metal oxides have been investi- in the case of performing SECM area scans under global sam-
52 gated as potential efficient electrocatalysts for photolelectro- ple irradiation, processes like degradation or photocorrosion of
53 chemical water oxidation,5 capable to promote the multi- the analyzed sample can influence the response obtained at the
54 electron OER driven by photon-generated holes.4 SECM tip. This is similarly the case for the recently proposed
Evidently, a better understanding of the properties and electro- SECCM platform for ultrasensitive photoelectrochemical
55
chemical processes involved in photoelectrochemical water imaging.16
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splitting will lead to the design and development of energy
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In order to overcome these issues, localized irradiation of the wafers coated with a 100 nm Pt layer. A target of elemental Ti
1 interrogated sample was introduced. A set-up for local illumi- (99.99 %) was used. The deposition was performed at a sub-
2 nation was developed in which an optical fiber of ~400 µm in strate temperature of 400 °C and a chamber pressure of 1.33
3 diameter was used instead of a tip microelectrode in a conven- Pa. The flows of reactive gas (O2) and sputter gas (Ar) were
4 tional SECM set-up for the analysis of different semiconductor adjusted to 90 and 30 sccm, respectively.
5 materials.6,10 The localized response at a semiconductor sur-
PREPARATION OF Bi-V-O SAMPLES
6 face could be evaluated by measuring the photocurrent pro-
7 duced at the analyzed surface during the scan of the optical The deposition of BiVO4 was performed on fluorine-doped tin
8 fiber along the sample. Yet, this strategy was only able to oxide (FTO) substrates (Pilkington, TEC 8A, 2.3 mm). Before
9 evaluate the photocurrent generated locally at the sample, use, the FTO substrates were cleaned with acetone in an ultra-
losing important information related to the electrochemical sonic bath for 5 min and in a 0.1 M NaOH bath at 75 °C for
10
properties of the interrogated sample surface with the SECM 15 min. After rinsing with water, the substrates were dried
11 tip. under an argon flow. All measurements were carried out in a
12 With the aim of combining the advantages of localized illumi- three-electrode set-up using a Ag/AgCl/3 M KCl (210 mV vs.
13 nation of the sample with SECM analysis of the surface, the NHE) as reference electrode and a platinum mesh as counter
14 set-up was further improved by Lee et al.17 using a commercial electrode. The preparation of BiVO4 films was performed
15 Au-coated optical fiber sealed in a glass capillary as SECM following a previously reported electrodeposition procedure.23
16 tip. By this, on the one hand the localized photocurrent re- Before deposition, the FTO substrates were modified with Pt-
17 sponse at the interrogated sample could be recorded. On the nanoparticles by applying a potential pulse profile in a 0.4 mM
18 other hand, the current recorded at the SECM tip could be H2PtCl6 solution with the purpose to decrease the overpoten-
19 additionally evaluated providing valuable information about tial for the electrodeposition of BiVO4. A no-effect potential
20 the reactivity of the analyzed samples.10,17,18 Examples of of 0 V was applied for 1 s followed by a deposition potential
21 application include rapid screening of arrays of catalysts drop- of -1 V for 0.2 s. The potential pulse profile was repeated 50
22 coated on a BiVO4-modified FTO substrate. In this case, the times. For BiVO4 deposition, a 0.54 M HNO3 solution con-
23 Au ring electrode at the tip was electrochemically plated with taining 35 mM VOSO4 and 10 mM Bi(NO3)3 was prepared,
Pt for the detection of O2 produced during water photooxida- increasing the pH value to 5 by adding 2 M sodium acetate
24
tion.4,10,19-21 Moreover, analysis of Ta3N5 nanotube arrays (VWR). After adjusting the pH value to 4.7 with concentrated
25
modified with several electrocatalysts for photoelectrochemi- HNO3, the electrodeposition was performed applying 1.9 V vs.
26 cal water oxidation was performed.7 Ag/AgCl/3 M KCl for 600 s at 70 °C using a heating bath
27 The comparably large dimensions of the ring electrode dictat- circulation thermostat. In order to avoid the precipitation of
28 ed by the size of the Au-coated optical fiber10 provided a ra- Bi0, the counter electrode was separated from the rest of the
29 ther low resolution in the currents recorded at the tip microe- solution by means of a membrane.
30 lectrode. Moreover, the possibility of using ring-shaped elec- Mo-doped BiVO4 samples were prepared by addition of 5 mM
31 trodes and of a restricted number of materials like gold or NaMoO4 to the precursor solution. For the preparation of
32 platinum, limit the applications of the available scanning pho- samples with a thickness gradient, BiVO4 was deposited while
33 toelectrochemical microscopy (SPECM) systems. slowly inserting the FTO substrate in the modification solution
34 We present a further improved SPECM set-up for the evalua- at a constant speed and simultaneously applying the anodic
35 tion of photoactive samples with increased resolution, capable potential for deposition. After that, the substrate was turned
36 of high-sensitive multi-purpose photoelectrochemical meas- 90° and inserted again in the Bi-V precursor solution contain-
37 urements. By coupling the light source into the microelectrode ing 2 mM NaWO4 or 2 mM NaMoO4, creating a thickness
38 capillary and using the glass sheath of the microelectrode as a gradient both in Bi and the doping metal (W or Mo, respec-
light guide, microelectrodes of different sizes and materials tively) as indicated in Figure S-1 (Supporting Information).
39
can now be used for the interrogation of different samples. In After deposition, the samples were annealed in air at 500 °C
40
this way, the proposed set-up is not limited by size, material for 1 h at a heating ramp of 2 K/min. Finally, the samples were
41 and geometry of the microelectrode as in previously reported cleaned from impurities in 1 M KOH for 20 min.
42 systems. The set-up was applied for the characterization of A thick layer of cobalt oxide (CoOx) used as light blocking
43 various photoanodes for water splitting. An important feature coating was deposited on Mo-doped BiVO4 (Figure S-2; SI)
44 is that the system was proved to provide a substantially higher from a 2 mM CoCl2 and 0.5 M KHCO3 pH 8.4 solution fol-
45 resolution of the currents recorded with the SPECM tip. This lowing a procedure as in 24. Briefly, the sample was mounted
46 characteristic was exploited for the analysis of complex photo- in an electrochemical cell with an opening of 0.5 cm in diame-
47 active samples. ter on one side and a quartz window on the other side. To
48 obtain a homogeneous and dense film of CoOx, the deposition
EXPERIMENTAL SECTION
49 was performed under illumination through the quartz window
50 All reagents were of analytical grade and used without further using a 150 W Hg-Xe lamp (Hamamatsu photonics). Addi-
51 purification. All chemicals were purchased from Sigma- tionally, a potential of 0.6 V (vs. Ag/AgCl/3 M KCl) was
52 Aldrich if not otherwise indicated. applied to facilitate the reduction reaction at the counter elec-
53 trode.
PREPARATION OF Ti-O SAMPLES
54 SCANNING PHOTOELECTROCHEMICAL MICROSCOPY
55 Sharp-edged TiO2 samples were prepared by reactive magne-
56 tron sputtering as described previously.22 Briefly, sputter dep- SPECM experiments were performed using a Ag/AgCl/3 M
osition was performed with a sputter system (AJA Int.) on Si KCl double junction reference electrode, a Pt cylindrical mesh
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counter electrode and a Pt microelectrode. The SPECM set-up SECM tip in x-, y-, and z-directions, a bipotentiostat (PGU-BI
1 is schematically shown in Figure 1A. The set-up is based on a 100, Jaissle), and a control software programmed using Visual
2 previously described SECM system,25 consisting of three step- Basic 6.0.
3 motor driven micrometer screws (Owis) for positioning of the
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Figure 1. (A) Representation of the scanning photoelectrochemical microscopy set-up used for local interrogation of semiconduc-
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tor-based photoactive samples. Inset, schematic diagram of the microelectrode used simultaneously for local illumination and as
21
sensing probe. CE: Counter electrode, RE: Reference electrode, WE: Working electrode. (B) Schematic drawing showing the di-
22 mensions of the Pt disk microelectrode and glass sheath used for local illumination. (C) The analysis of semiconductor samples for
23 water splitting under illumination was performed by collecting evolved oxygen at a Pt microelectrode polarized at an adequate
24 potential for ORR.
25
26 The tip microelectrode was used for localized irradiation of point of the scanned grid of an SECM array scan experiment.
27 the interrogated substrate and simultaneously as a probe for During the scan a given potential was applied to the interro-
28 the detection of evolved oxygen during water photooxidation gated sample and tip by a bipotentiostat. The tip was then
29 at the semiconductor sample. A 150 W Hg-Xe lamp (LC8, positioned at a predefined distance from the sample and the
30 Hamamatsu photonics) was coupled to the end of the tip mi- surface was scanned. The duration of a full area scan was
31 croelectrode by means of a light fiber (HITRONIC® POF between 40 min and 3.5 h. The measured tip current and sam-
Simplex PE). In this way, the glass sheath of the microelec- ple photocurrent produced a color-coded image of the scanned
32
trode acts as an extended light-guide allowing focalizing the surface.
33
radiation on the interrogated area just below the microelec-
34 trode tip. The Pt microelectrode was fabricated following a
RESULTS AND DISCUSSION
35 procedure described elsewhere26 using 25 µm Ø Pt wire ANALYSIS OF SEMICONDUCTOR M ATERIALS
36 (Goodfellow). In order to allow an adequate amount of light to
37 reach the analyzed surface, the microelectrodes were fabricat- In order to prove the capability of the developed system for
38 ed with an RG value of about 8 (Figure 1B). The top end of the interrogation of photocatalyst surfaces, different semicon-
39 the glass capillary was sealed and polished for coupling of the ductor materials for photoelectrochemical water oxidation
40 light fiber (Figure 1A). The effective light intensity which were evaluated.
41 reaches the sample surface was measured to be 0.35 mW
42 which corresponds to a light intensity of 280 mW cm‒2. The
43 sample was placed in a Teflon SECM cell sealed with an O-
44 ring exposing an area of about 1.5 cm². Before starting the
45 analysis of the modified surfaces, the tip was positioned in
46 close proximity to the analyzed sample by recording z-
approach curves in air-saturated buffer. For this, the tip was
47
polarized at -600 mV vs. Ag/AgCl/3 M KCl for the steady-
48 state measurement of the oxygen reduction reaction (ORR).
49 The tip was then approached to the sample surface while re-
50 cording the tip current. In order to avoid any possible interfer-
51 ence from the sample on the current recorded at the tip during
52 the z-approach, the sample was kept unbiased, thus behaving
53 as an electrochemically inactive surface leading to negative
54 feedback approach curves. For distance control during the Figure 2. Difference in tip current recorded under light and dark
55 scan, z-approach curves were recorded at three x-, y- coordi- during an area scan of BiVO4 deposited on an FTO substrate.
56 nates and the tilt of the sample surface was calculated. The z- Sample polarized at +200 mV vs. Ag/AgCl/3 M KCl (910 mV vs.
distance was corrected using the calculated tilt plane at each RHE). A 25 µm Ø Pt tip polarized at -600 mV vs. Ag/AgCl/3 M
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KCl was used for ORR detection. Area scan at constant distance strate. (A) Stripe of Mo-doped BiVO4 of about 100 µm width; (B)
1 of about 20 µm from the surface. x,y grid increment: 20 µm. Mo-doped BiVO4 deposited on the left region of the substrate; (C)
2 Electrolyte: 0.1 M phosphate buffer, pH 8.5. Mo-doped BiVO4 deposited on the left region of the substrate
3 with a CoOx catalyst deposited additionally on top of the bottom
As a result of the localized illumination through the microelec- half of the sample. The schemes on the right side illustrate the
4 trode tip coupled to the irradiation source, we were able to composition of the modified surfaces. Sample polarized at +200
5 obtain 2D-maps of local photocatalytic activity of the investi- mV vs. Ag/AgCl/3 M KCl (910 mV vs. RHE). The scan was
6 gated sample. Moreover, information about the semiconductor recorded with a 25 µm Ø Pt tip polarized at -600 mV vs.
7 behavior for water oxidation was derived by collecting locally Ag/AgCl/3 M KCl for ORR. Area scan at constant distance of the
8 evolved O2 at the tip (Figure 1C). For the evaluation of the tip SPECM tip about 20 µm from the surface. x,y grid increment: 10
9 current at each grid point of the scanned area, the dark current µm. Electrolyte: 0.1 M phosphate buffer, pH 8.5.
10 was subtracted from the current measured under illumination.
The tip current was therefore only related to the collection of In the area scan, the high resolution of the tip current allowed
11 to detect regions of different catalytic activity on a uniform
12 oxygen formed upon illumination of the sample preventing
any contributions from dark reactions. Two different ap- semiconductor layer as a result of a microscopic inhomogenei-
13 ty of the sample.
14 proaches were evaluated to obtain the difference plots for tip
current and sample photocurrent. Either the steady state cur- Further evaluation of the SPECM set-up was performed by the
15 investigation of different Bi-V-O samples. First, a Mo-doped
rent at each grid point of the scan area was recorded under
16 BiVO4 stripe of about 100 µm width deposited on an FTO
dark and illumination before moving the tip to the next x,y-
17 grid point, or two successive full scans were recorded under substrate was analyzed. In Figure 3A a clear contrast is shown
18 light and dark conditions. No significant differences were between the two different regions of the sample. With the
19 observed using both approaches (data not shown); however, SPECM tip located above the unmodified FTO a minimum
20 for long scans the second approach was preferred to avoid cathodic current at the tip was measured, while higher cathod-
21 possible sample degradation of the applied bias potential. ic O2 collection currents were recorded with the tip positioned
22 The results obtained proved the ability for the interrogation of above the Mo-doped BiVO4 stripe upon illumination. The
23 the sample with a microelectrode probe while simultaneously edge of a Mo-doped BiVO4 layer deposited on FTO was also
investigated (Figure 3B). The ORR tip current drastically
24 collecting data from the photocurrent at the sample, where the
tip microelectrode acts at the same time as source for localized increased when the microelectrode was positioned above FTO
25
irradiation of the evaluated surface and for the collection of modified with the semiconductor as a consequence of the high
26 activity for water splitting of the locally illuminated Mo-doped
27 generated species (i.e., evolved O2).
As an example, Figure 2 shows the SECM surface scan image BiVO4 region. Moreover, a sample consisting of the edge of a
28 Mo-doped BiVO4 layer deposited on FTO was additionally
29 of a BiVO4 thin film deposited on an FTO substrate. The pho-
tocurrent increase was consistent with an increased water modified with a cobalt oxide (CoOx) water oxidation catalyst
30 (Figure 3C). The modified sample comprised four different
oxidation to O2 at local hot-spots of the deposited semiconduc-
31 regions, including bare FTO, Mo-doped BiVO4-modified
tor.
32 FTO, bare FTO with CoOx, and Mo-doped BiVO4-modified
33 FTO modified with a CoOx layer. Higher cathodic currents
34 were recorded with the Pt tip positioned above the left side of
35 the scanned area, corresponding to the region modified with a
36 deposited Mo-doped BiVO4 film. The maximum cathodic
37 current was observed if the microelectrode was positioned
38 above the region modified with both Mo-doped BiVO4 and
CoOx at the bottom left of the analyzed area, where CoOx acts
39
as electrocatalyst for water oxidation.4 In contrast, the CoOx
40
on FTO area at the bottom right only exhibits a slight increase
41 in cathodic tip current. Moreover, as expected, the unmodified
42 FTO substrate provided the lowest tip current. The obtained
43 results encouraged us to evaluate the limits in resolution of the
44 tip current during illumination of a semiconductor.
45
46 HIGH RESOLUTION SPECM
47 A higher lateral resolution of the locally recorded photocur-
48 rents as well as ORR tip currents was expected as compared
49 with previously suggested systems due to the small surface of
50 the used SPECM tip. Considering the spatial resolution of a
51 system as the smallest distance between two different areas of
52 a sample which are represented in an SECM image by signifi-
53 cantly different currents,27 the resolution was evaluated by
54 scanning across the sharp edge of a TiO2 layer deposited by
sputter coating on a Pt-modified silicon wafer. Figure 4 shows
55
Figure 3. Difference in tip current recorded under light and dark the corresponding high lateral resolution both for the sample
56
for different semiconductor samples deposited on an FTO sub- photocurrent as well as the ORR current recorded at the
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SPECM tip. To exclude topography effects from the sample, pends on the distance between the sample and the tip. This
1 this scan was recorded using the ORR current measured under effect was evaluated by performing line scans over the sharp
2 dark as feedback signal for positioning of the microelectrode edge of the deposited semiconductor (Figure S-3; SI). The
3 at a constant tip-to-sample distance during the whole experi- obtained results indicate that the maximum resolution was
4 ment. During the scan the tip and sample currents were rec- reached with the microelectrode tip positioned at short tip-to-
5 orded at the end of sequential dark and light periods at each sample distances of up to 20 µm from the surface. Moreover,
6 analyzed grid point and the difference in current under light the resolution in the collection of evolved O2 with the tip
7 and dark was calculated. The small dimensions of the SPECM microelectrode was evaluated by comparing the ORR obtained
8 tip allowed for a high-resolution collection of evolved O2 in a line scan performed over the edge of the semiconductor
9 (Figure 4A), in contrast to a negligible difference in tip reduc- (Figure S-4; SI) providing as expected a lateral resolution limit
tion current when the tip was positioned above the unmodified determined by the tip radius27 of ∆x/r = 6.7.
10
substrate. Due to the localized irradiation of the sample sur- The versatility of the implemented set-up allows to easily
11 face the photocurrent recorded at the modified sample could increase the spatial resolution by simply decreasing the size of
12 also be simultaneously precisely measured (Figure 4B). The the SECM tip used for performing the scan. While for the
13 local sample photocurrent is in very good agreement with the examples shown here a 25 µm Ø Pt tip provided a sufficiently
14 determined activity for O2 evolution as shown in Figure 4A. high resolution, the dimensions of the tip electrode can be
15 The TiO2 layer exhibited a thickness gradient along the y decreased if needed for the analysis of more complex samples.
16 direction, therefore leading both to an increasing ORR tip
17 ANALYSIS OF COMPLEX PHOTOACTIVE SAMPLES
current as well as an increasing photocurrent along the y-
18 coordinates. Further studies were performed by analyzing a sample com-
19 prised of a 5 mm diameter spot of photo-electrodeposited
20 CoOx on previously electrodeposited Mo-doped BiVO4. In this
21 case, the intentionally thick layer of CoOx acts as just as a
22 blocking coating, preventing the radiation from reaching the
23 underlying Mo-doped BiVO4 layer. The sample was polarized
24 at a potential sufficient for light induced water splitting by the
25 deposited Mo-doped BiVO4, but low enough to prevent direct
water oxidation at the CoOx spot in the dark. Therefore, only
26
regions of the sample with exposed Mo-doped BiVO4 are
27
showing light-induced water oxidation. No detection of O2 is
28 expected when the tip is positioned on top of the CoOx spot.
29 The sample was first evaluated by recording line scans over
30 the CoOx spot, with the tip positioned at different distances
31 from the sample surface (Figure S-5; SI). For larger tip-to-
32 sample distances (> 20 µm), a lower ORR current is recorded
33 at the tip when it was positioned on top of the CoOx spot, thus
34 leading to a lower contrast among the different regions in the
35 recorded line scan.
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48 Figure 4. (A) Difference in tip current and (B) sample photocur-
49 rent recorded during an area scan of the edge of a TiO2 layer
50 deposited on a Pt-modified silicon wafer. Sample polarized at 400
51 mV vs. Ag/AgCl/3 M KCl (1023 mV vs. RHE). The area scan
was recorded using a 25 µm Ø Pt tip polarized at -600 mV vs.
52
Ag/AgCl/ 3 M KCl for ORR. Scan at constant distance of about
53 10 µm from the surface. x,y grid increment: 25 µm. Electrolyte:
54 0.1 M phosphate buffer, pH 7.0.
55
56 Interestingly, as the tip is used simultaneously as source of
irradiation, the resolution of the recorded photocurrent de-
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Bi-V with a thickness gradient in metal composition as illus-

1 trated in Figure S-1 (SI).
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22 Figure 6. Difference in tip current (A, C) and sample photocur-
rent (B, D) recorded during the surface scan of W-Bi-V (A, B)
23 and Mo-Bi-V (C, D) samples prepared with a thickness gradient
24 in metal loading as indicated in Figure S-1. Sample polarized at
25 489 mV vs. Ag/AgCl/3 M KCl (1230 mV vs. RHE). The scan was
26 Figure 5. Tip current recorded during an area scan of a Mo-doped recorded with a 25 µm Ø Pt tip polarized at -600 mV vs.
27 BiVO4 sample on FTO with a spot of about 5 mm Ø of photode- Ag/AgCl/3 M KCl for ORR. Scan at constant distance of about 20
28 posited CoOx. (A) Scan without illumination, (B) scan with irradi- µm from the surface. x,y grid increment: 1000 µm. Electrolyte:
ation, (C) difference in tip current between (B) and (A). Sample 0.1 M borate buffer pH 9.0.
29 polarized at 0.0 mV vs. Ag/AgCl/3 M KCl (980 mV vs. RHE).
30 The scan was recorded with a 25 µm Ø Pt tip polarized at -600 As previously demonstrated,28 the thickness of the deposited
31 mV vs. Ag/AgCl/3 M KCl for ORR. Scan at constant distance of semiconductor layer is directly related to the deposition time
32 about 20 µm from the surface. x,y grid increment: 100 µm. Elec- in the precursor solution for the formation of the semiconduc-
33 trolyte: 0.1 M KOH. tor layer in the modification of FTO substrates (Figure S-6;
34 SI). The thickness gradient in metal composition of the modi-
The highest contrast was observed when the tip was positioned
35 fied samples was evaluated by EDX analysis of an FTO sub-
20 µm above the interrogated sample. This distance was se-
36 strate modified with the W-Bi-V system. The obtained results
lected for performing area scans of the sample surface (Figure
37 presented in Figure S-7 (SI), for the different analyzed regions
5).
38 on the gradient line for W-Bi, show an increased deposition
In the dark, the current recorded at the tip was negligible, only
39 time directly related with a higher loading of semiconductor,
allowing to visualize the CoOx spot due to small changes in
as inferred from a higher intensity in the characteristic ele-
40 the tip current caused by topographic effects (Figure 5A).
mental peaks. Thus, confirming the presence of a thickness
41 Under irradiation, the semicircular spot of the deposited CoOx
gradient in the prepared samples.
42 on top of the Mo-doped BiVO4 sample becomes visible. The
For analysis of thickness-gradient samples with the SPECM
43 O2 collection current recorded at the tip increases when the tip
set-up, the tip was scanned over a large area of the modified
44 was positioned above the Mo-doped BiVO4 modified sub-
surfaces recording simultaneously the response at the sample
45 strate, while a negligible current for oxygen collection at the
under local illumination and the collected evolved O2. The
46 tip was obtained when the microelectrode was positioned
differences in tip current and sample photocurrent after the
above the circular spot of CoOx (Figure 5B). In Figure 5C the
47 analysis of both semiconductor samples is depicted in Figure
difference in tip current recorded under light and dark is pre-
48 6, while the individual values obtained during the scan under
sented. A clear edge between the two different regions is ob-
49 light and dark conditions are presented in Figure S-8 (SI) for
served, in accordance with the microscope image of the modi-
50 the W-Bi-V sample and in Figure S-9 (SI) for the Mo-Bi-V
fied surface (Figure S-2; SI) and demonstrating the capability
51 sample.
for the collection of evolved O2 with the SPECM tip used
52 Interestingly, the highest photoelectrocatalytic activity for
simultaneously for localized irradiation of the sample.
53 light induced oxygen evolution is related to smaller thickness-
The SPECM was additionally applied for the analysis of semi-
54 es of the BiVO4 layer. At thick films both the tip current and
conductor materials with a thickness gradient (Figure 6). The
sample photocurrent decreased, indicating a reduced produc-
55 two analyzed samples were prepared as described in the Ex-
tion of molecular oxygen. This can be explained by the limit-
56 perimental Section, comprising the systems W-Bi-V and Mo-
ing impact of electron diffusion to the back contact for thick
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layers of BiVO4, resulting in high rates of recombination of ACKNOWLEDGMENTS

1 the photogenerated electron/hole pairs. Moreover, a higher This work was supported by the Cluster of Excellence RESOLV
2 activity was observed for the Mo-doped sample in comparison (EXC 1069) and in the framework of the SPP 1613
3 with the W-containing system, as can be inferred when the (SCHU929/12-1, 12-2) funded by the Deutsche Forschungsge-
4 intensities in the recorded sample photocurrent and tip current meinschaft (DFG).
5 are compared, suggesting an increased activity for Mo-doped
6 samples under the same conditions. REFERENCES
7 CONCLUSIONS (1) Cook, T. R.; Dogutan, D. K.; Reece, S. Y.; Surendranath, Y.;
8 Teets, T. S.; Nocera, D. G. Chem. Rev. 2010, 110, 6474–6502.
9 The proposed SPECM set-up allows the local interrogation (2) Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.;
and analysis of photoactive samples, as shown exemplarily for Mi, Q.; Santori, E. A.; Lewis, N. S. Chem. Rev. 2010, 110,
10 6446–6473.
the analysis of photoanodes for water splitting. The use of a
11 (3) Chen, X.; Shen, S.; Guo, L.; Mao, S. S. Chem. Rev. 2010, 110,
microelectrode tip for simultaneous local irradiation of the
12 6503–6570.
analyzed sample and as SECM probe for the collection of
13 (4) Ye, H.; Park, H. S.; Bard, A. J. J. Phys. Chem. C 2011, 115,
electroactive species provides a high lateral resolution both, at 12464–12470.
14 the sample photocurrent and at the tip current. Moreover, as (5) Galán-Mascarós, J. R. ChemElectroChem 2014, 2, 37–50.
15 the glass sheath of the microelectrode is used as light guide, (6) Liu, G.; Liu, C.; Bard, A. J. J. Phys. Chem. C 2010, 114,
16 virtually all electrode materials and dimensions are possible to 20997–21002.
17 use. (7) Cong, Y.; Park, H. S.; Wang, S.; Dang, H. X.; Fan, F.-R. F.;
18 The high contrast obtained for the collection of evolved oxy- Mullins, C. B.; Bard, A. J. J. Phys. Chem. C 2012, 116, 14541–
19 gen can be directly related with the sample photocurrent, mak- 14550.
(8) Park, H. S.; Leonard, K. C.; Bard, A. J. J. Phys. Chem. C 2013,
20 ing the developed system of particular interest for the screen-
117, 12093–12102.
21 ing of libraries of OER-catalysts bearing different catalyst (9) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, 2nd edn.;
22 loadings. John Wiley & Sons, Inc., 2001.
23 The resolution of the system for the collection of electroactive (10) Lee, J.; Ye, H.; Pan, S.; Bard, A. J. Anal. Chem. 2008, 80,
24 evolved species was proved to be superior when compared to 7445–7450.
25 previous systems and it is expected that even a higher resolu- (11) Kemp, T. J.; Unwin, P. R.; Vincze, L. J. Chem. Soc. Faraday T.
tion could be attained by decreasing the surface of the Pt mi- 1995, 91, 3893–3896.
26 (12) Haram, S. K.; Bard, A. J. J. Phys. Chem. B 2001, 105, 8192–
croelectrode, if necessary. Consequently, the implemented
27 SPECM set-up is suggested as a powerful tool for high- 8195.
28 resolution analysis and characterization of different photoac-
(13) Fonseca, S. M.; Ahmed, S.; Kemp, T. J.; Unwin, P. R. Photo-
29 chem. Photobiol. Sci. 2003, 2, 98.
tive samples. (14) Harati, M.; Jia, J.; Giffard, K.; Pellarin, K.; Hewson, C.; Love,
30
D. A.; Lau, W. M.; Ding, Z. Phys. Chem. Chem. Phys. 2010,
31 ASSOCIATED CONTENT 12, 15282–15290.
32 (15) Zigah, D.; Rodríguez-López, J.; Bard, A. J. Phys. Chem. Chem.
Supporting Information
33 Phys. 2012, 14, 12764–12772.
34 Supporting Information Available: Additional figures including a (16) Aaronson, B. D. B.; Byers, J. C.; Colburn, A. W.; McKelvey,
scheme for the prepared binary samples with thickness gradient, K.; Unwin, P. R. Anal. Chem. 2015, 87, 4129–4133.
35
microscope image of CoOx deposited on Mo-BiVO4, photocur- (17) Lee, Y.; Bard, A. J. Anal. Chem. 2002, 74, 3626–3633.
36 rents recorded while moving the microelectrode tip at different (18) Lee, Y.; Ding, Z.; Bard, A. J. Anal. Chem. 2002, 74, 3634–
37 distances from the surface, evaluation of the resolution limit of the 3643.
38 tip microelectrode, tip current plots recorded at different tip-to- (19) Ye, H.; Lee, J.; Jang, J. S.; Bard, A. J. J. Phys. Chem. C 2010,
39 sample distance, SEM image for thickness gradient evaluation, 114, 13322–13328.
40 EDX analysis of gradient W-Bi-V sample, tip and sample currents (20) Liu, W.; Ye, H.; Bard, A. J. J. Phys. Chem. C 2010, 114, 1201–
recorded under dark and light for W-Bi-V, tip and sample currents 1207.
41 (21) Cho, S. K.; Park, H. S.; Lee, H. C.; Nam, K. M.; Bard, A. J. J.
42 recorded under dark and light for Mo-Bi-V. (PDF)
Phys. Chem. C 2013, 117, 23048–23056.
This material is available free of charge via the Internet at
43 (22) Sliozberg, K.; Schäfer, D.; Erichsen, T.; Meyer, R.; Khare, C.;
http://pubs.acs.org.
44 Ludwig, A.; Schuhmann, W. ChemSusChem 2015, 8, 1270–
45 1278.
AUTHOR INFORMATION (23) Seabold, J. A.; Choi, K.-S. J. Am. Chem. Soc. 2012, 134, 2186–
46 2192.
47 Corresponding Author
(24) Spataru, N.; Terashima, C.; Tokuhiro, K.; Sutanto, I.; Tryk, D.
48 *E-Mail: wolfgang.schuhmann@rub.de A.; Park, S.-M.; Fujishima, A. J. Electrochem. Soc. 2003, 150,
49 Tel.: +49 234 3226200 Fax: +49 234 3214683 E337-E341.
50 (25) Ballesteros Katemann, B.; Schulte, A.; Schuhmann, W. Chem.
Author Contributions Eur. J. 2003, 9, 2025–2033.
51 (26) Kranz, C.; Ludwig, M.; Gaub, H. E.; Schuhmann, W. Adv.
52 The manuscript was written through contributions of all authors. Mater. 1995, 7, 38–40.
53 All authors have given approval to the final version of the manu- (27) Wittstock, G.; Emons, H.; Ridgway, T. H.; Blubaugh, E. A.;
54 script. Heineman, W. R. Anal. Chim. Acta 1994, 298, 285–302.
55 Notes (28) Fahoume, M.; Maghfoul, O.; Aggour, M.; Hartiti, B.; Chraïbi,
F.; Ennaoui, A. Sol. Energ. Mat. Sol. C. 2006, 90, 1437–1444.
56 The authors declare no competing financial interest.
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