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JIEC 4030 No. of Pages 7

Journal of Industrial and Engineering Chemistry xxx (2018) xxx–xxx

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry


journal homepage: www.elsevier.com/locate/jiec

Upgraded organic vapor treatment and hydrogen generation using


low-cost metal/1D black titania nanocomposites under simulated solar
irradiation
Yeon-Ji Jin, Wan-Kuen Jo*
Department of Environmental Engineering, Kyungpook National University, Daegu, 702-701, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history:
Received 7 December 2017 Photocatalytic processes are attractive techniques in environmental waste treatment and renewable
Received in revised form 11 May 2018 energy generation. Herein, earth-abundant transition metal (Fe, Cu, or Ni)-impregnated one-dimensional
Accepted 29 May 2018 black TiO2 nanocomposites showed upgraded photocatalytic activities in vapor decomposition and
Available online xxx hydrogen production compared with reference samples. These results were ascribed to enhanced charge-
separation efficiencies, as demonstrated by photoluminescence emission spectroscopy and hydroxyl
Keywords: radical density measurements, and/or enhanced visible-light-absorption efficiencies. The photocatalytic
Earth-abundant metal activities depended on the initial concentration of pollutant and relative humidity in the case of pollutant
Nanostructure
decomposition, whereas they depended on the type and composition of the hole scavenger in the case of
Environmental degradation
hydrogen production.
Photocatalytic hydrogen production
Hole scavenger © 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction orange in water and in hydrogen evolution [6]. Pt-augmented black


TiO2 nanoparticles, prepared by a magnesiothermic reduction
Photocatalytic processes using TiO2 are widely used in process, also produced high levels of photocatalytically evolved
environmental waste treatment and renewable energy generation. hydrogen [7]. In addition, hybrid g-C3N4/black TiO2 nanostruc-
However, a major drawback of this approach is that TiO2 can only tures, fabricated by a hydrogenation process, showed enhanced
be activated efficiently under ultraviolet (UV) light exposure, photocatalytic performance in the decomposition of organic
limiting the use of the visible region of solar light [1,2]. contaminants [8]. The enhanced photocatalytic activities were
Modification of TiO2 by hydrogenation to obtain black TiO2 is an mainly attributed to modified surface properties and electronic
attractive technique to overcome this problem [3,4]. Several types structures, such as the presence of a disordered surface lattice and
of black TiO2-based photocatalysts have shown enhanced optical oxygen vacancies, and a narrowed band gap [4].
properties and photocatalytic activities when used in pollutant The geometrical configuration of a nanostructured photo-
decomposition and hydrogen production [3,5–8]. Specifically, catalyst is another important factor that determines its photo-
Chen et al. reported that black TiO2 particles (BTiO2) incorporating catalytic efficiency [9,10]. Although zero-dimensional (0D)
Pt, fabricated using a hydrogenation process, showed high photo- spherical photocatalysts have excellent specific surface areas for
catalytic efficiencies in the degradation of aqueous phenol and contaminant adsorption, they suffer from fast charge carrier
methylene blue, as well as in hydrogen production, under visible- recombination, resulting in low quantum yields. This shortcoming
light illumination [3]. A black TiO2-based nanoarchitecture can be overcome by transforming spherical nanoparticles into one-
prepared under hydrogen-flow conditions showed improved dimensional (1D) nanostructures with higher surface-to-volume
photocatalytic performance for the decomposition of vaporous ratios, which facilitate interfacial charge transport and hole–
acetaldehyde under visible light exposure [5]. BTiO2 with a core/ electron separation [1]. Using the synergistic effect of high visible-
shell nanostructure, produced using hydrogen plasma, exhibited light absorption by black TiO2 and the high surface-to-volume
excellent photocatalytic performance in the oxidation of methyl ratios of 1D structures, 1D black TiO2 nanotube arrays have been
developed with enhanced photocatalytic activities for pollutant
decomposition and hydrogen generation [11–14].
* Corresponding author. Furthermore, doping TiO2 with metals can enhance its
E-mail address: wkjo@knu.ac.kr (W.-K. Jo). photocatalytic activities in pollutant degradation and hydrogen

https://doi.org/10.1016/j.jiec.2018.05.046
1226-086X/© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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JIEC 4030 No. of Pages 7

2 Y.-J. Jin, W.-K. Jo / Journal of Industrial and Engineering Chemistry xxx (2018) xxx–xxx

generation [15,16]. Upon doping with metal cations, an Metal-impregnated BTNT was prepared by impregnating the
intermediate electronic level is formed in the prohibited band BTNT sample with a metal (Fe, Cu, or Ni). Fe(NO3)39H2O (98%),
of TiO2, which narrows the band gap and thus allows this Cu(NO3) 3H2O (99%), and Ni(NO3)26H2O (99.99%) were utilized as
photocatalyst to effectively absorb visible light. In addition, the the Fe, Cu, and Ni sources, respectively. A specific weight of each
metal dopant impurities can serve as electron traps, which metal source (calculated to give metal-impregnated BTNT samples
suppress the recombination of charge carriers. Therefore, with a metal-to-BTNT loading of 0.01) was added to 10 mL of
impregnation of 1D black TiO2 nanostructures with metals deaerated water and stirred for 2 h, after which 1 g of BTNT powder
may generate unique photocatalysts with enhanced photo- was added and stirred for 2 h. This suspension was kept at 20–25  C
catalytic performance. To address this hypothesis, we investi- for 12 h, dried at 85  C for 10 h, and calcined at 300  C for 2 h. The
gated the photocatalytic activities of metal-impregnated 1D final product was cooled and ground to obtain the metal-
black TiO2 nanostructures for the decomposition of vaporous impregnated BTNT powder. Fe-, Cu-, and Ni-impregnated BTNT
pollutant (1,2,4-trimethyl benzene) under simulated-solar- samples were designated as FeBTNT, CuBTNT, and NiBTNT,
light illumination. Instead of utilizing expensive noble metals, respectively. In addition, NiBTNT samples with Ni-to-BTNT
three earth-abundant transition metals (Fe, Cu, and Ni) were loadings of 0.05, 0.10, and 0.20 were prepared and designated as
used. The target compound was chosen because of its high NiBTNT-0.05, NiBTNT-0.10, and NiBTNT-0.20, respectively.
detection frequency in indoor environments and its hazardous The fabricated materials were characterized using X-ray
properties [17]. diffraction (XRD, Rigaku D/max-2500 diffractometer), high-reso-
Hydrogen is a green energy resource, because its combustion lution transmission electron microscopy (HRTEM, FEI Titan G2
does not generate either CO2 or other toxic pollutants. However, ChemiSTEM Cs Probe TEM), UV-visible spectroscopy (Varian CARY
fossil fuels are generally used for the industrial hydrogen 5G), X-ray photoelectron spectroscopy (XPS, PHI Quantera SXM),
production, which is not environmentally favorable. Alternatively, and photoluminescence (PL) emission spectroscopy (Acton Re-
photocatalytic water splitting for hydrogen production with solar search SpectraPro 2150i). Detailed photocurrent measurement
energy has also received considerable interest as a sustainable procedures are provided in the supplementary content.
green process [18,19]. Photocatalytic hydrogen production can be
performed using a renewable solar energy source. This green Contaminant decomposition test
hydrogen energy can be utilized as a fuel for a variety of hydrogen-
energy systems, such as internal combustion engines in hydrogen- The photocatalytic decomposition of 1,2,4-trimethyl benzene
fueled cars, fuel cells, and thermal power generators. Although using the fabricated photocatalysts under simulated-solar-light
certain amounts of methanol are used for the photocatalytic irradiation was assessed in a continuous flow reactor (effective
hydrogen production, the photocatalytic process still provides volume, 0.21 L) (Supplementary Fig. S1) according to the procedure
more environmental as well as economic benefits than typical used in our previous study [20]. In brief, the interior surface of the
fossil-fuel-based industrial processes. Nevertheless, the use of reactor was covered with a nominal weight of each photocatalyst
expensive noble metals as co-catalysts in many metal oxide- (0.2 mg cm 2) and a daylight lamp was placed inside the reactor.
semiconductor-based photocatalysts has limited their practical The irradiance intensity was recorded as 1.7 mW cm 2 at the
application. Therefore, we investigated photocatalytic hydrogen photocatalyst surface. An ultra-pure air stream was supplied from
production using a low-cost transition metal-impregnated black a compressed gas cylinder and divided into dry and humidity-
TiO2 nanotubes (BTNT) sample under simulated solar irradiation. saturated air stream lines. The humidity was controlled by
For comparison, the photocatalytic activities of reference TiO2 adjusting the mixing ratio of humidity-saturated air to dry air.
particles, BTiO2, TiO2 nanotubes (TNT), and BTNT samples in The humidity-controlled air was delivered to a buffering bottle
pollutant decomposition and/or hydrogen production were also (1 L) to decrease any fluctuation in the air flow and then mixed
evaluated. with 1,2,4-trimethyl benzene in a mixing chamber. The mixed
standard gas, with an initial 1,2,4-trimethylbenzene concentration
Experimental of 10, 20, 40, or 50 ppm, was infused into the photocatalytic reactor.
The control procedures included system cleaning, continuous
Photocatalyst fabrication monitoring of the relative humidity and the adsorption equilibri-
um of 1,2,4-trimethyl benzene, and a photolysis test. The details of
TNT was fabricated from P25 TiO2 powder using a hydrothermal the sampling and analytical methods, along with hydroxyl radical
process. In brief, 1.0 g of P25 TiO2 powder (<20 nm) was added to density measurement methods, are provided in the supplementary
60 mL of deionized water and stirred to obtain a homogeneous material.
solution, after which 21 g of sodium hydroxide was added and
stirred for 20 min. The resulting suspension was transferred to a Hydrogen production test
Teflon bottle vessel, hydrothermally treated at 120  C for 48 h, and
cooled to 20–25  C. This mixture was centrifuged, and the obtained Photocatalytic water splitting for hydrogen evolution was
precipitates were added to 100 mL of 0.1 M hydrochloric acid, performed using a 70 mL Pyrex reactor with a quartz window. A
stirred for 12 h, and washed with distilled water. The washed mixture of Na2S (0.2 M, 15 mL)/sodium sulfite (Na2SO3, 0.2 M,
precipitate was filtered, dried at 85  C for 15 h, and annealed at 15 mL), methanol (30 mL)/distilled water (30 mL), ethanol (30 mL)/
350  C for 1 h to obtain the TNT powder. distilled water (30 mL), or lactic acid (30 mL)/deionized water
BTNT was fabricated by hydrogenating the as-synthesized TNT (30 mL) was transferred into the reactor, and then the synthesized
powder. Briefly, TNT powder was transferred into an alumina boat photocatalyst (30 mg) was added. These solutions were employed
and placed in a tubular electric furnace. Hydrogenation was carried to minimize the backward reaction of H2 and O2 to H2O on the
out by setting the H2 (5%)/Ar flow rate to 500 mL min 1, heating the catalyst surface [18,19]. Subsequently, the mixture was purged for
furnace to 350  C at a rate of 2  C min 1, and then maintaining these 30 min by bubbling pure nitrogen gas and then irradiated at an
conditions for 5 h. The hydrogenated TiO2 was washed with intensity of 1 Sun using a solar simulator with a 300 W xenon lamp.
distilled water, filtered, and dried at 85  C for 6 h to obtain the BTNT Gas samples were collected periodically using a gas-tight syringe
sample. BTiO2 was prepared by hydrogenating P25 TiO2 powder via (500 mL) and analyzed using a gas chromatograph (Shimadzu GC-
the procedure used for BTNT synthesis. 2010) equipped with a capillary column (Carboxen 1010 PLOT).

Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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Results and discussion Table 1


Wall thickness and inner diameter of TNT, BTNT, CuBTNT, FeBTNT, and NiBTNT
samples.
Catalyst characteristics
Photocatalyst Wall thickness Inner diameter
(nm) (nm)
Fig. 1 exhibits the HRTEM images of TNT, BTNT, FeBTNT, CuBTNT,
and NiBTNT, which reveal that all samples maintained their TNT 2.6 4.6
BTNT 2.7 4.9
nanotubular morphology and exhibited thermal stability after
CuBTNT 2.9 4.6
annealing at 350  C for 1 h. These samples were open-ended, with FeBTNT 3.0 4.6
wall thicknesses of 2.6–3.0 nm and inner diameters of 4.6–4.9 nm NiBTNT 2.8 4.7
(Table 1). However, annealing at temperatures above 400  C may
transform the nanotubular morphology into nanorods or nano-
particles [21,22]. All samples showed a lattice distance of 0.189 nm, and the Ni 2p3/2 and Ni 2p1/2 peaks at 856.1 and 871.2 eV,
which is associated with the (200) plane of the anatase phase. The respectively, corresponded to Ni2+ [23]. In contrast, none of these
XRD patterns of the TNT-based photocatalysts (TNT, BTNT, FeBTNT, metals were observed in the unmodified TNT sample (Supplemen-
CuBTNT, and NiBTNT) also revealed a major peak at 2u = 48.5 tary Fig. S3).
corresponding to the (200) plane of the anatase phase (Supple- The XPS spectra in the Ti 2p region for the TNT, as-prepared
mentary Fig. S2). In contrast, the TiO2 and BTiO2 samples exhibited NiBTNT, and used NiBTNT samples suggested the presence of Ti4+
both anatase and rutile phases. Notably, these results indicate that in TNT and used NiBTNT, but the formation of Ti3+ species in as-
the rutile phase of TiO2 and BTiO2 was transformed to the anatase prepared NiBTNT (Supplementary Fig. S4). In the XPS spectra of
phase in photocatalysts. Unlike the XRD patterns of 0D spherical TNT and used NiBTNT, 2p1/2 and Ti 2p3/2 peaks appeared at binding
TiO2 and BTiO2, the TNT-based samples exhibited weak or no energies of 464.1 and 458.4 eV, respectively, which could be
intensities for the anatase and rutile phase peaks at 2u = 25.3 and ascribed to the presence of Ti4+. Conversely, these peaks appeared
27.2 , respectively, which is in accordance with the results reported at lower binding energies (463.7 and 458.0 eV for Ti 2p1/2 and Ti
in previous studies [11,21]. Additionally, the hydrogenated photo- 2p3/2, respectively) for as-prepared NiBTNT, which could be
catalysts (BTNT, FeBTNT, CuBTNT, and NiBTNT) had both a attributed to the presence of Ti3+ [7,23]. These results indicated
disordered amorphous layer and a TiO2 crystallite phase, whereas that the Ti3+ ions in as-prepared NiBTNT are unstable and are
the TiO2 sample had only a crystallite phase, consistent with the photooxidized to Ti4+ during the photocatalytic reaction.
results obtained for other hydrogenated TiO2-based catalysts [3,7]. Fig. 3 displays the valence band XPS spectra and band energy
For these samples, the disordered layers located outside the TiO2 diagrams for TiO2, FeBTNT, CuBTNT, and NiBTNT. Each of the
crystallite core are marked with a dot-lined box in Fig. 1. The hydrogenated photocatalysts had two valence band levels (1.36
disordered amorphous layer can yield mid-gap states, increasing and 2.38 eV for FeBTNT; 1.34 and 2.36 eV for CuBTNT; and 1.34 and
visible-light absorption and thus photocatalytic performance [4,7]. 2.36 eV for NiBTNT), whereas the bare TiO2 had only one (2.84 eV)
The HRTEM mapping results showed the presence of Fe, Cu, and (Fig. 3a). These results revealed the formation of two band gaps for
Ni in the FeBTNT, CuBTNT, and NiBTNT samples, respectively, the hydrogenated samples and one band gap for bare TiO2 (Fig. 3b),
indicating that these metals were well impregnated into the BTNT consistent with the double and single slopes, respectively,
powder (Fig. 2). Moreover, the XPS spectra demonstrated that the observed in the corresponding UV-visible absorption curves
metals present in these samples were ions, not neutral atoms (Fig. 4). The conduction band minima of the synthesized photo-
(Supplementary Fig. S3). The Fe 2p3/2 and Fe 2p1/2 peaks observed catalysts were estimated using the slopes in the magnified figure of
at 710.3 and 722.1 eV, respectively, matched Fe2+; the Cu 2p3/2 and the valence-band XPS spectra shown in Fig. 3. The upward tailing of
Cu 2p1/2 peaks at 932.1 and 952.3 eV, respectively, matched Cu2+; the valence bands were obtained from the second slopes in the

Fig. 1. HRTEM images of TNT, BTNT, FeBTNT, CuBTNT, and NiBTNT.

Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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Fig. 2. Mapping of FeBTNT, CuBTNT, and NiBTNT.

Fig. 3. (a) Valence-band XPS spectra and (b) band energy diagrams of TiO2, BTNT, FeBTNT, CuBTNT, and NiBTNT.

intensity vs binding energy curve (Fig. 3a), creating narrowed band The UV-visible absorption spectra of TiO2, BTiO2, TNT, BTNT,
gaps in the samples. CuBTNT, FeBTNT, and NiBTNT are displayed in Fig. 4. The
The metal-impregnated BTNT samples were synthesized using absorption spectra of TiO2 and TNT revealed low absorption
a metal doping process. Neither metals nor metal oxides were efficiencies in the visible region. By contrast, the hydrogenated
observed on the surfaces of the metal-impregnated BTNT samples samples exhibited enhanced absorption efficiencies in the visible-
(Fig. 1). The band gaps of the metal-impregnated BTNT samples light range, which were assigned to modified surface properties
were narrower than that of the unmodified BTNT sample (Fig. 3). and electronic structures [3,4,6]. Moreover, the visible-light-
These results were attributed to the formation of intermediate absorption efficiencies of two of the metal-impregnated hydroge-
electronic levels in the metal-impregnated BTNT samples between nated samples (FeBTNT and NiBTNT) were higher than that of the
the conduction and valence bands, likely owing to the presence of bare hydrogenated sample without metal impregnation (BTNT)
the metals as metal ion dopants in the bulk, which modifies the owing to the localized or delocalized electronic states produced by
BNT electronic structure. Consequently, the metals in the metal- the impregnated metals [23–26]. However, CuBTNT had a lower
impregnated BTNT samples are most likely ion dopants in the bulk. visible-light-absorption efficiency than BTNT, probably due to the

Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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Fig. 6. Photoluminescence emission spectra of TiO2 particle, BTiO2 particle, TNT,


Fig. 4. UV-visible absorption spectra of TiO2, BTiO2, TNT, BTNT, FeBTNT, CuBTNT, BTNT, CuBTNT, FeBTNT, and NiBTNT samples.
and NiBTNT.
light-absorption efficiencies (Fig. 4). The higher degradation
absorption of light by excess Cu; further investigation is suggested efficiencies of FeBTNT and NiBTNT compared with that of BTNT
to confirm this phenomenon. The visible-light-absorption effi- were ascribed to both enhanced charge-separation efficiencies and
ciencies of the synthesized catalysts were in the order of: visible-light-absorption efficiencies, as the visible-light-absorp-
TiO2 < BTiO2 < CuBTNT < BTNT < FeBTNT < NiBTNT, which is con- tion efficiencies of FeBTNT and NiBTNT were also higher than that
sistent with the order of catalyst blackness (Supplementary of BTNT. However, the higher degradation efficiency of CuBTNT
Fig. S5). compared with that of BTNT was ascribed mainly to enhanced
charge-separation efficiency, as the visible-light-absorption effi-
Photocatalytic decomposition efficiencies ciency of CuBTNT was lower than that of BTNT. The metal dopants
(Fe, Cu, and Ni) might increase the charge carrier mobility or serve
The adsorption and photocatalytic degradation efficiencies of as charge-carrier traps, thus increasing the life times of the charge
1,2,4-trimethyl benzene vapor over the synthesized samples under carriers in FeBTNT, CuBTNT, and NiBTNT, respectively [27–29].
simulated-solar-light irradiation are shown in Fig. 5. Adsorption of It is noteworthy that the XPS spectra of TNT and used NiBTNT
the target pollutant on the surfaces of the catalysts, which was revealed the existence of Ti4+, whereas the spectrum of as-
performed under dark conditions, was not significant (<5%). In synthesized NiBTNT indicated the presence of Ti3+, suggesting
addition, a control photolysis experiment performed using an that Ti3+ ions present in as-prepared NiBTNT were unstable and
uncoated reactor revealed no significant photodegradation of this photooxidized to Ti4+ during photocatalysis (Supplementary
contaminant. As the photocatalytic decomposition of 1,2,4- Fig. S4). Nevertheless, the photocatalytic activities of NiBTNT
trimethyl benzene was assessed using a continuous-flow reactor, for 1,2,4-trimethyl benzene decomposition and hydrogen pro-
the time-series photocatalytic decomposition efficiencies reflect duction did not change significantly over the 5 h photocatalytic
the hourly stability of the photocatalysts. The extent of photo- process, likely owing to favorable properties other than the
catalytic degradation was found to vary, depending on the formation of Ti3+, such as structural disorder and a narrowed band
photocatalyst. The photocatalytic degradation efficiencies were gap [25]. Similarly, Koo et al. reported that a blue TiO2-based
in the order of: TiO2 < BTiO2 < TNT < BTNT < FeBTNT < CuBTNT < photocatalyst displayed Ti3+ instability during a photoelectro-
NiBTNT, which is in agreement with the order of corresponding chemical process, but it still exhibited enhanced activities for 4-
charge-separation efficiencies, as indicated by the PL spectra chlorophenol degradation and hydrogen production, which were
(Fig. 6). NiBTNT also revealed a higher photocurrent response than not affected by multiple uses [25].
pure TiO2, which further demonstrated its enhanced carrier- Hydroxyl radical (OH) density measurements confirmed the
separation efficiency (Supplementary Fig. S6). The higher degra- enhanced charge separation efficiency of NiBTNT compared with
dation efficiencies of BTiO2 and BTNT compared with those of bare those of BTNT and BTiO2 (Fig. 7). The peak intensities of the
TiO2 and TNT, respectively, were ascribed to their increased visible- fluorescence spectra of BTiO2, BTNT, and NiBTNT increased
gradually as the illumination time increased from 30 to 60 min,
indicating an increase in 2-hydroxyterephthalic acid (2HTPA)
concentration over time. In addition, the peak intensity of NiBTNT
was higher than that of BTNT, which in turn, was higher than that
of BTiO2. As OH is produced primarily by the reaction of positive
holes with hydroxyl ions/water molecules and its concentration is
proportional to the 2HTPA concentration [30,31], NiBTNT would be
expected to show a higher concentration of positive holes than
BTNT and BTiO2 owing to improved charge-separation efficiencies.
The effects of the initial concentration of 1,2,4-trimethyl
benzene on degradation efficiency using NiBTNT under simulat-
ed-solar-light irradiation were investigated. The degradation
efficiency of vaporous 1,2,4-trimethyl benzene over NiBTNT
decreased gradually as the initial concentration increased from
10 to 50 ppm (Supplementary Fig. S7). This trend was attributed to
increased competition of the target pollutant at high initial
Fig. 5. Degradation efficiencies of vaporous 1,2,4-trimethyl benzene over TiO2,
BTiO2, TNT, BTNT, CuBTNT, FeBTNT, and NiBTNT under simulated solar light
concentrations. Similarly, Jo and Kang reported that the degrada-
irradiation. tion efficiencies of vaporous limonene over multiwalled carbon

Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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Fig. 7. Fluorescence spectra of BTiO2, BTNT, and NiBTNT for 2HTPA for three different light illumination times (30, 45, and 60 min).

nanotube-incorporated TiO2 nanofibers under daylight illumina- time-series hydrogen evolution rates for NiBTNT-0.1 with different
tion decreased as the initial concentration increased [32]. types of hole scavengers under simulated-solar-light irradiation. For
Using an initial concentration of 50 ppm, the photocatalytic each hole scavenger (10 vol% in deionized water), the hydrogen
degradation efficiencies of NiBTNT samples with different Ni-to- evolution rate over NiBTNT-0.1 increased gradually as the irradiation
BTNT loadings were determined. The degradation efficiency of the time increased, but varied depending on the type of hole scavenger.
target pollutant increased as the Ni-to-BTNT loading increased In contrast, hydrogen production by BTNT was not detected over the
from 0.01 to 0.1, but decreased when the Ni-to-BTNT loading was 5-h photocatalytic period, regardless of the type of hole scavenger.
increased further to 0.2, indicating an optimal Ni composition for The 5-h average hydrogen evolution rates corresponding to the hole
NiBTNT photocatalysts (Supplementary Fig. S8). The decreased scavengers were in the order of: lactic acid (187 mmol g 1 h 1) >
degradation efficiency of the NiBTNT sample with a Ni-to-BTNT methanol (168 mmol g 1 h 1) > ethanol (128 mmol g 1 h 1) >
loading of 0.2 was ascribed to an increased charge-carrier glycerol (107 mmol g 1 h 1). Similarly, Lingampalli et al. reported
recombination rate owing to the formation of recombination sites that hydrogen yields with ZnO/Pt/CdS under visible-light irradia-
by excess Ni on the catalyst surface. tion depended on the type of hole scavenger. These results
demonstrated that the type of hole scavenger is an important
Photocatalytic hydrogen generation factor in photocatalytic hydrogen evolution processes [33].
Fig. 9 exhibits the time-series hydrogen evolution rates for
Photocatalytic hydrogen evolution procedures were carried out NiBTNT-0.1 according to the volume of lactic acid in deionized
using NiBTNT-0.1, as this sample exhibited the highest 1,2,4- water under simulated-solar-light irradiation. The 5-h average
trimethyl benzene decomposition efficiency. Fig. 8 displays the hydrogen evolution rates increased from 126 to 187 mmol g 1 h 1

Fig. 8. Time-series hydrogen evolution rates (mmol g-1) by BTNT and NiBTNT-0.1 Fig. 9. Time-series hydrogen evolution rates (mmol g-1) by NiBTNT-0.1 according to
according to the type of hole scavenger (methanol (10%), ethanol (10%), lactic acid volume percentage of lactic acid to deionized water (5, 10, 15, and 20%) under
(10%), and glycerol (10%) under simulated solar light irradiation. simulated solar light irradiation.

Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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The initial concentration of the target pollutant and the relative


humidity of the air stream were shown to be important operational
factors in the photocatalytic decomposition of pollutants by the
metal-impregnated 1D BTiO2 nanostructures. Additionally, the types
and amounts of hole scavenger were important parameters for
photocatalytic hydrogen production.

Acknowledgements

This work was supported by the National Research Foundation


of Korea (NRF) grant funded by the Korea government (MSIP) (No.
2016R1A2B4009122 and 2017R1A4A1015628).

Disclosure statement
Fig. 10. Schematic band structures of TiO2 and NiBTNT, and the reduction–
oxidation. The author declares that no conflicting actual or potential
interests exist.
as the amount of lactic acid increased from 5 to 10 vol%; however,
the rates decreased to 145 and 50 mmol g 1 h 1 upon further Appendix A. Supplementary data
increasing the lactic acid amount to 15 and 20 vol%, respectively,
indicating the optimal amount of lactic acid for photocatalytic Supplementary data associated with this article can be found, in
hydrogen evolution over NiBTNT-0.1. Other research groups have the online version, at https://doi.org/10.1016/j.jiec.2018.05.046.
used lactic acid concentrations of 10–90 vol% for photocatalytic
hydrogen generation [34,35]. Specifically, Chen et al. [34] added a References
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Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046

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