Feature

Cite This: Environ. Sci. Technol. 2019, 53, 2937−2947 pubs.acs.org/est

The Technology Horizon for Photocatalytic Water Treatment:

Sunrise or Sunset?
Stephanie K. Loeb,†,‡ Pedro J. J. Alvarez,†,§ Jonathon A. Brame,∥ Ezra L. Cates,⊥ Wonyong Choi,#
John Crittenden,¶ Dionysios D. Dionysiou,□ Qilin Li,†,§ Gianluca Li-Puma,■ Xie Quan,○
David L. Sedlak,● T. David Waite,△ Paul Westerhoff,†,▽ and Jae-Hong Kim*,†,‡
†
Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (NEWT) 6100 Main Street, MS 6398,
Houston, Texas 77005, United States
‡
Department of Chemical and Environmental Engineering and, Yale University, 17 Hillhouse Avenue, New Haven, Connecticut
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

06511, United States

§
Department of Civil and Environmental Engineering, Rice University, 6100 Main Street, Houston, Texas 77005, United States
∥
US Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Road, Vicksburg, Mississippi 39180, United
States
Downloaded via 77.49.117.39 on September 7, 2023 at 15:55:12 (UTC).

⊥
Department of Environmental Engineering and Earth Sciences, Clemson University, 342 Computer Court, Anderson, South
Carolina 29625, United States
#
Division of Environmental Science and Engineering, Pohang University of Science and Technology, Pohang 37673, Korea
¶
Brook Byers Institute for Sustainable Systems, School of Civil and Environmental Engineering, Georgia Institute of Technology,
Atlanta, Georgia 30332, United States
□
Environmental Engineering and Science Program, Department of Chemical and Environmental Engineering, 705 Engineering
Research Center, University of Cincinnati, Cincinnati, Ohio 45221-0012, United States
■
Environmental Nanocatalysis & Photoreaction Engineering, Department of Chemical Engineering, Loughborough University,
Loughborough, LE11 3TU, United Kingdom
○
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science
and Technology, Dalian University of Technology, Dalian 116024, China
●
Department of Civil & Environmental Engineering and Engineering Research Center for Reinventing the Nation’s Urban Water
Infrastructure (ReNUWIt), University of California, Berkeley, California 94720, United States
△
School of Civil and Environmental Engineering, University of New South Wales, Sydney New South Wales 2052, Australia
▽
School of Sustainable Engineering and The Built Environment, Arizona State University, Box 3005, Tempe, Arizona 85287,
United States

ABSTRACT: Advanced oxidation processes via semiconductor photocatalysis

for water treatment have been the subject of extensive research over the past
three decades, producing many scientific reports focused on elucidating
mechanisms and enhancing kinetics for the treatment of contaminants in
water. Many of these reports imply that the ultimate goal of the research is to
apply photocatalysis in municipal water treatment operations. However, this
ignores immense technology transfer problems, perpetuating a widening gap
between academic advocation and industrial application. In this Feature, we
undertake a critical examination of the trajectory of photocatalytic water
treatment research, assessing the viability of proposed applications and
identifying those with the most promising future. Several strategies are proposed
for scientists and engineers who aim to support research efforts to bring
industrially relevant photocatalytic water treatment processes to fruition.
Although the reassessed potential may not live up to initial academic hype, an
unfavorable assessment in some areas does not preclude the transfer of
photocatalysis for water treatment to other niche applications as the technology
retains substantive and unique benefits.

Published: December 21, 2018

© 2018 American Chemical Society 2937 DOI: 10.1021/acs.est.8b05041

Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

■ INTRODUCTION
Imagine a still image of the sun hanging low in the horizonis
it rising or setting? Only by examining subsequent time lapse
images can we predict its future direction. The development of
a new technology follows a similar path but of unknown length,
rising from its initial conception to reach a zenith of popularity
before arcing back toward the horizon. Photocatalytic
advanced oxidation processes (AOPs) for water treatment
have traveled a long path of technological development, having
been the subject of extensive research over the past 35 years.
Conventional AOPs employ precursor chemical oxidants, such
as O3 and H2O2, in combination or with an input of energy
(e.g., ultraviolet (UV) irradiation), to produce reactive oxygen
species (ROS) for the oxidative destruction of contaminants in
water. Heterogeneous semiconductor photocatalysis enables
advanced oxidation via a fundamentally different mechanism:
photons with energy equal to or greater than the material’s
band gap are absorbed by a particulate catalyst resulting in the
formation of a conduction band electron (e−cb) and valence
band hole (h+vb) pair. Although both e−cb and h+vb can participate
in a suite of redox reactions relevant to water treatment,
hydroxyl radicals (•OH), both surface-bound and in bulk
phase, are considered the dominant oxidant.1 Historically
adapted from the discovery of photoelectrochemical water-
splitting at the surface of a TiO2 electrode,2 photocatalysis was Figure 1. Publications trends in photocatalytic water treatment
quickly recognized for its potential in water treatment.3,4 research. Web of Science results for the number of yearly publications
The advantages of photocatalytic water treatment over on photocatalytic water treatment from 1999 to 2017. Inset shows
homogeneous-phase AOPs are well documented. The bench- detailed results from the most recent complete reporting year (2017),
mark commercial semiconductor material, TiO2, is inexpensive with each search keyword (i.e., “TiO2”, “visible”, “reactor”, and
(∼$1/kg),5 physically robust, and relatively nontoxic. It “pilot”) modifier added to “photocatal* water treatment” individually.
Results indicate that only a small fraction of publications consider
requires low-energy ultraviolet light (UV-A) for excitation, reactor design or pilot scale investigations.
allowing for potential solar applications. As a heterogeneous
catalytic process, it obviates the need to continuously supply
precursor chemicals, which is a striking benefit for some (booming) academic research and (modest) industrial
applications particularly those in remote or resource-limited application. Consequently, skepticism has grown, leading
locations. A recent surge in scientific literatureover 8000 some to question whether photocatalysis will become a
articles since 2000on the topic of photocatalytic water mainstream water treatment technology within the next two
treatment reflects this optimism (Figure 1). Despite substantial decades.
research over the past few decades, the application of Among the foremost roadblocks identified, low photo-
photocatalysis in practical water treatment systems has been conversion efficiency remains a major challenge. Each step of
very limited compared to conventional AOPs. Considering the photoconversion process has an associated loss of
these trends, how should the research community view the efficiency, as detailed in Figure 2. Consistently, quantum
technology horizon of photocatalytic water treatment? In this yields (Φ) reported in the literature, while varying widely
Feature, we examine the current status of heterogeneous depending on the photocatalysts and experimental conditions,
semiconductor photocatalytic water treatment, emphasizing are a few percent at most, even when measured using a probe
barriers to technology transfer, examining the feasibility of substrate with monochromatic irradiation near the band gap
practical applications, and identifying key research needs for (Table 1 inset in Figure 2). Compared to other AOPs, such
overcoming obstacles, in search of answers to this question. low Φ for •OH production is considered the most critical

■ FUNDAMENTAL ROADBLOCKS PREVENTING

TRANSFER OF RESEARCH TO PRACTICE
drawback in photocatalytic water treatment. Taking UV/H2O2
AOPs as an example, the photolytic decomposition of H2O2 in
organic-free water at 254 nm has a reported Φ of 50%, and a
The difficulties impeding commercial success of photocatalytic resulting •OH production yield near 100%,17,18 making it very
AOPs are evidenced by the small number of systems currently challenging for photocatalysis to compete in terms of energy
being used in water treatment practice. This is at odds with an efficiency. However, it should be noted that TiO2 can absorb
abundance of literature reporting the use of photocatalysis for photons in the less energetic UV-A range, permitting the use of
the treatment of common surface and groundwater pollutants. sunlight, and it does not require H2O2 addition, which is a
Typically performed at bench-scale, these studies tend to over- major cost in conventional AOPs.
represent the opportunities and under-represent the limitations As an additional limitation inherent to all AOPs, only a small
demonstrated by the technology when applied in the field. An fraction of generated ROS contributes to the eventual
overemphasis on material design and mechanistic evaluations destruction of target pollutants. The high reactivity (∼109
has led to some hubris in the academic literature regarding the M−1 s−1 for many organic contaminants)19 and nonspecificity
practicality of photocatalysis, perpetuating the gap between of •OH is generally considered an advantage of AOPs over
2938 DOI: 10.1021/acs.est.8b05041
Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

Figure 2. Detailing the low-energy conversion efficiencies in typical TiO2 photocatalytic water treatment processes. Photons are generated either by
electrical conversion or directly harnessing solar energy. (1a) Although low-pressure mercury lamps are typical, blue/UVA LEDs are being
increasingly studied, with wall plug efficiencies nearing 30%.6 (1b) Electrical conversion losses are obviated when harnessing solar energy; however,
< 5% of solar photons are absorbed as the wide band gap (Eg = 3.0−3.2 eV; 390−410 nm) of TiO2 is poorly matched to the solar spectrum.7 (2)
Photons entering the reactor can be lost through intrinsic scattering by the particulate and inefficient light management leading to catalytic
absorption of 30−70% of the photons emitted into a typical slurry reactor.8 (3) Photons absorbed by the catalyst can then produce e−cb and h+vb,
which further perform redox reactions at the catalyst surface to generate ROS. Regardless of the source of light, a majority (>90%) of
photogenerated e−cb/h+vb pairs recombine rapidly (within subμs),4,9 leading to quantum yields (Φ) of less than 10% for most materials. The inset
table shows a list of experimentally reported bench-scale material Φ for •OH production from various TiO2 photocatalysts.10−16 (4) The
availability of generated ROS for pollutant destruction is greatly decreased through scavenging. As an illustration, a representative estimate of
natural water containing 3 mg-C/L (k(•OH) = 108 L/mol-C·s) and 50 mg/L of bicarbonate alkalinity as CaCO3 (k(•OH-HCO3−) = 8.5 × 107 /M·
s) suggests that <5% of •OH would be available compared to distilled water (i.e., in the absence of scavengers) at the same pH.

other treatment systems. However, the presence of natural photocatalytic activity.23 Indeed, TiO2 has retained a central
organic matter (NOM), carbonate species, and other back- locus in photocatalytic materials science research, which
ground constituents can greatly limit the effectiveness of continues to concentrate on two major limitations of TiO2
photocatalytic processes by scavenging ROS and absorbing as avenues for improving catalyst performance: limited
light (Figure 2).20,21 Studies conducted at pilot and full-scale absorption and the high recombination rate of photogenerated
have indeed observed these effects to be exacerbated by the primary species e−cb and h+vb.
presence of multiple interfering compounds coexisting at Many notable augmentations to TiO2 have been achieved.
variable concentrations.22 Although engineering and materials Extending the photoactivity to lower energy wavelengths was
science are poised to make significant efficiency improvements, first realized by the incorporation of transition metals (e.g., Fe,
inherent constraints of the technology cannot be neglected Cr, and V),24,25 and later by introducing nonmetal dopants
when translating new research advances to industrial (e.g., N, C, F, and S)26 to create oxygen vacancies or low lying
applications. interband states at the localized energy levels of the dopant. In

■ EFFORTS TO ADVANCE PHOTOCATALYTIC

MATERIALS
a recent leap-ahead application of this approach, surface
hydrogenation was employed to create many disorder-induced
midgap states, upshifting the valence band-edge, resulting in
Limited industry adoption has done little to suppress the black/blue-colored TiO2 crystals with absorption near the
steady flow of studies focused on the development of new infrared region.27 Though effective at improving absorption of
photocatalytic materials. Inspired by advances in materials visible light, too many midgap states can lead to excessive
science and nanotechnology, an increasingly larger portion of recombination and an overly narrowed band structure,
research has sought to develop improved catalyst materials. reducing the redox potential of the e−cb/h+vb pair and impacting
Early efforts began with modifications to anatase TiO2. For the type of ROS produced.28 The formation of heterojunctions
example, flame pyrolysis synthesis of the well-known P25 TiO2 with smaller band gap semiconductors29 or sensitization with
powder is not only economical at industrial scale, but has been organic chromophores30 can also widen the absorption toward
found to result in a minority rutile phase fraction, improving visible light. Similarly, visible light-absorbing noble metal
2939 DOI: 10.1021/acs.est.8b05041
Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

Figure 3. Select reactor designs for semiconductor photocatalytic water treatment: (a) A typical slurry reactor system consisting of a reactor
containing suspended TiO2 photocatalysts with a quartz encased LP Hg UV light source and membrane filtration for catalyst recovery. (b−d) More
recently developed reactor designs incorporating immobilized catalyst particles obviating the need for post-treatment membrane separation.

nanoparticles can inject electrons into the photocatalyst WO3) is able to produce •OH under visible light through
conduction band.31 multielectron reduction by the in situ generation and
Junctions with metals have also been extensively employed subsequent decomposition of H2O2.40 A newly emerging
to reduce recombination, acting as electron withdrawing alternative, BiPO4 has a more positive valence band maximum
centers through the formation of a rectifying Schottky potential than TiO2 resulting in increased oxidation power,
barrier.32 However, high loadings of cocatalysts can limit the higher photoactivity, and greater efficiency of mineralization at
surface area, complicate the synthesis procedure, and result in a the expense of requiring higher energy UV excitation.41
physically fragile composite material. This same composite Creative and yet-to-be-devised solutions are required to
architecture can be achieved by replacing metals with translate these promising materials into practical water
semimetallic carbonaceous materials such as graphene,33 but treatment applications. These fundamental research efforts,
the intrinsic instability of these materials in an oxidative which have been further detailed in a number of
environment remains an unresolved challenge. Nanoscale comprehensive reviews,42−44 continue to result in better
control over structural hierarchy and porosity present addi- materials while deepening our knowledge of semiconductor
tional opportunities to improve the efficiency of TiO2 by
photocatalytic treatment.
promoting charge migration and increasing surface area.34−36
Considering the depth of high-quality research conducted to
Many researchers continue to focus on improving the
advance photocatalysis materials science, it is prudent to
performance and stability of these augmented TiO2 materials.
scrutinize why TiO2 has yet to be superseded by a next-
Beyond modifications to TiO2, other semiconductor
materials have been investigated as substitutes for TiO2. CdS generation material. A primary challenge in the field is
and WO3 are relatively effective visible light photocatalysts, but identifying a threshold requirement for replacement; what
toxic components such as Cd are clearly incongruent with safe determines whether a breakthrough material is “better” than
and sustainable water treatment practices. Graphitic carbon TiO 2 ? Beyond bench-scale evaluation, many practical
nitride (C3N4) is a metal-free visible light photocatalyst with a challenges have been overlooked in research that focuses on
tunable electronic structure,37,38 though it exhibits poor novel materials development. Our review of the literature
chemical stability. Hybrid organic−inorganic perovskite reveals a proliferation of scientifically interesting, yet
materials offer a structural platform for highly tailored impractical materials that are fragile, chemically unstable, or
absorption/charge transport properties using low cost, earth- have expensive, rare, or inherently toxic components.
abundant materials.39 Increasingly popular in the solar cell Evaluation conditions that more completely reflect industrial
literature, a major limitation of perovskites in environmental application by expanding performance criteria beyond
applications has been instability in wet conditionsclearly a absorption (i.e., greater spectral match and less scattering)
drawback for water treatment. Some materials have emerged as and quantum yield (i.e., reduced recombination) to include
viable alternatives to TiO2: platinized tungsten oxide (Pt/ cost of production, long-term stability, robustness, ease of
2940 DOI: 10.1021/acs.est.8b05041
Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

separation, and other application specific conditions, would aid performance of new materials and reactor designs. Photo-
in technology transfer. catalytic water treatment represents a highly variable parameter

■ PHOTOCATALYTIC REACTOR DESIGN AND

SYSTEM EVALUATION
space that depends on target pollutant, water quality
parameters, reaction time, mixing conditions, and light source.
To ease knowledge transfer, uncoupling reaction rate constants
The focus of academic research on materials development from the number of photons absorbed is critical. Determi-
rather than reactor or systems engineering arguably overlooks nation of LVRPA is integral for flow-through reactor design,
opportunities to improve the performance of photocatalytic although it has not been deemed necessary for material
water treatment systems through innovative reactor design. evaluations typically performed in a well-mixed batch reactor.
Despite numerous studies in this area, 45 the sparse If we accept at a minimum that characterization of new
configurations in practice have largely been restricted to catalysts should include measurements of Φ, then a concerted
reactor systems with light emitted into a slurry of well-mixed effort to quantify the number of photons in the system, by
TiO2 particles to maximize photon absorption and mass either radiometry or chemical actinometry, is essential, as this
transfer of redox species,46 as shown in Figure 3a. These information cannot be derived from reporting irradiation time
systems may be competitive with other AOPs in selected niche and lamp type/power alone. Depending on the proposed
applications discussed below; however, they remain unopti- application and method of evaluation, this Φ may be defined in
mized and suffer from limitations including low energy terms of target pollutant destruction or the generation of a
efficiency, slow reaction kinetics, and in selected cases, catalyst specific oxidizing species such as •OH. Care should be taken to
fouling or photoaggregation.22,47 Alternatively, photocatalysts consider whether the reactions in a particular system may
can be immobilized onto support substrates, eliminating the occur via bulk-phase or surface-bound •OH, or through
need for ultrafiltration separation and reducing shear stress on pathways involving other oxidative species. Additionally, for
catalyst particles. The efficiency of immobilized systems, accurate reporting of kinetics, a probe compound that does not
however, can be further limited by obscured catalyst surface compete for absorption nor degrade with direct photolysis
area, reduced illuminated catalyst surface area per volumetric should be employed. For these reasons, as well as their
water treated, and higher rates of photon scattering. susceptibility to sensitization, dyes, such as methylene blue, are
Immobilization substrates explored (Figure 3b−d) include inappropriate probes for comparing the activity of photo-
optical fibers for improved light management48 and fluidized catalytic semiconductors.59
media,49 foam porous supports,50 membranes,51 and electro-
Effective comparison is challenging not only among different
spun fibers,52 which have each been engineered to improve
photocatalytic systems, but between photocatalysis and its
pollutant destruction while minimizing ROS scavenging. The
competitor AOP technologies. The most commonly applied
majority of these immobilized reactor designs remain at bench
figure of merit is electrical energy per unit order (EE/O): the
scale or in conceptual phase. Recent rapid advances in light
emitting diode (LED) technology are poised to inspire a new electric energy (or alternatively the area of solar radiation)
generation of innovative reactor designs due to their required to degrade a target contaminant by 1 order of
advantageous over gas discharge lamps including less fragile magnitude in a unit volume of contaminated water.60 For a
casings, lack of toxic components, small size, and rapid warm- treatment scenario with low-concentration of target contam-
up time.53,54 inants compared to background scavengers, EE/O is
The relatively slow translation of these studies to industrial straightforward to calculate, and is a versatile aid to design.
practice is likely related to the complexity of large-scale system Translation from bench-, to pilot-, to full-scale applications can
design, something often overlooked at bench scale. Such therefore be readily assessed through determination and
barriers, however, have not limited increasingly widespread, reporting of EE/O for common pollutants. While values of
full-scale adoption of UV and UV/H2O2 water purification ∼<0.5 to 10 kWh/m3 are considered competitive for drinking
applications,55 which likewise require radiation field determi- water applications,60 typical slurry TiO2/UV systems tend to
nation. Radiation scattering by the catalyst makes it report values of 10 kWh/m3 or higher, whereas competing
cumbersome to assess the local volumetric rate of photon AOPs such as UV/H2O2 and H2O2/O3 can report less than 1
absorption (LVRPA) at each point within a photocatalytic kWh/m3.22,61 Although reporting of EE/O or other metrics,
reactor by analytically or numerically solving the radiation such as electron efficiency,62 is encouraged, the limitations of
transfer equation (RTE). In a simplified approach, the six-flux- comparing technologies using a single value should be
model (i.e., following scattered photons routed through the six recognized. Care should be taken to include other factors as
directions of the Cartesian coordinates) has been successful in well, such as the embedded energy requirements (or costs) of
calculating LVRPA at accuracies close to the RTE while applying consumable chemicals.

■
allowing for the derivation of dimensionless parameters useful
in slurry reactor design.47,56,57 Ray-tracing, which involves STRATEGIES FOR IMPROVING RESEARCH
analyzing the path of individual rays from an emission source OUTCOMES
based on the optical properties of the incident environment,
has previously been applied to determine local radiation fields When recent advances in materials science and reactor
in UV disinfection reactors.58 This technique could be adapted engineering are combined, opportunities to improve the
to determine LVRPA in immobilized photocatalyst reactors performance of photocatalytic water treatment may emerge.
with relative ease, although incorporating an absorbing and On the basis of our collective experience, we propose the
scattering mobile particulate slurry into a ray tracing analysis following strategies for researchers aiming to advance photo-
presents a nontrivial challenge. catalytic water treatment processes without succumbing to the
Other difficulties result from the lack of a universally pitfalls that have stunted progress during the past three
accepted method to quantitatively evaluate and compare the decades:
2941 DOI: 10.1021/acs.est.8b05041
Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

(1) Expand the criteria for assessing the performance of scale, reports show the EE/O of UV/H2O2 tends to be
photocatalytic water treatment systems. To create tech- significantly lower than UV/TiO2.22,64 Aside from energy
nologies that have a higher likelihood of attracting efficiency, homogeneous AOPs are easier to engineer, are not
commercial interest, researchers should expand perform- surface area limited, have fewer mass transfer problems, and do
ance criteria to include factors such as material cost and not experience catalyst surface fouling. For large scale
availability, the feasibility of large-scale production, municipal applications, it is the agreement among industry
tendency to foul in the proposed water matrix, and practitioners, as well as these authors, that current photo-
long-term stability and performance under likely catalytic water treatment systems are impractical because they
operating conditions. are less efficient and have higher costs than existing UV/H2O2,
(2) Evaluate the performance of photocatalysts under well- O 3 /H2 O 2, and UV/O3 technologies. 65,66 However, an
defined conditions. The use of established approaches for unfavorable prospect for large scale application does not
quantifying photon fluence and absorption (e.g., radio- preclude the potential of photocatalysis for water treatment in
metry, actinometry, or computational evaluation of select niche applications; the technology still retains sub-
LVRPA) is essential, as is the use of probe compounds stantive and unique benefits. Tangible short-term outputs
that do not affect light absorption or otherwise alter the based on a valid business model and a clear pathway for
catalyst.59 As candidate photocatalysts advance toward technology transfer to industry are overdue, considering the
practical application, testing should be done under maturity of basic science and, indeed, are critical to shrink the
standardized conditions, using well-characterized probe increasingly wider gap between industrial needs and academic
compounds, and solution conditions (e.g., pH, ionic research.
composition, concentration of ROS scavengers) that Reappraising the unique benefits of photocatalysis over
approximate those encountered in actual treatment other AOPs may pave the road toward these niches. For
systems. An appropriate figure of merit, such as EE/ example, photocatalysis enables not only oxidation but also
O,60 should be reported when comparing the efficiency reduction, presenting relatively untapped opportunities to
of different AOPs. reductively remove oxyanions, such as nitrate,67 chromate,68
(3) Consider creative approaches and seek break-through and redox-active metal ions, such as Ag+.69 For several metals,
photocatalysts without neglecting the challenges of adapting reduction can lead to irreversible fouling through the
materials f rom other disciplines. While repurposing formation of crystallites on the surface of the catalyst.69 In
emerging materials from related fields can be an effective contrast, Cr(VI) can be reduced to less toxic Cr(III) which is
strategy to develop innovative water treatment photo- easily precipitated out of solution.70 This process can be made
catalysts, a blind pursuit can lead to the promotion of more favorable by the presence of abundant efficient h+
materials not suitable for practical AOP application. For scavengers.71 Innovative approaches to improve the reductive
example, materials developed for water-splitting or use of photocatalysis continue to emerge,72 albeit still in
photovoltaics also operate under photoinduced charge embryonic phase. The ability to reduce oxygen to form H2O2
transfer processes; however, they differ in the nature of by select photocatalysts, such as C3N4,73 may also become a
their energy conversion processes and are designed with useful approach to produce AOP precursors on site.
different ideal characteristics in mind. As such, even the Through the oxidation pathway, the generation of highly
most successful of these materials may be ineffective at oxidative h+vb in addition to ROS can contribute to degradation
generating ROS for water treatment. of recalcitrant organics and even mineralization for niche
(4) Design and test materials for specif ic applications. Many applications.74 Photocatalysis has been proposed as a pretreat-
past reports on photocatalyst performance fail to identify ment for particularly challenging waters, especially those that
the most appealing application for the material. The occur in smaller volumes compared to municipal waste
performance of a photocatalyst depends upon the streams; for example, effluents loaded with lignin (in the
properties of the contaminant being treated,63 as well pulp and paper mill industry),75 dyes (textile industry),76 poly/
as the relative concentrations of other interfering perfluoroalkyl substances (chemical industry),77,78 and pesti-
components. As a result, researchers may develop cides (pharmaceutical industry).79−81 While reducing toxicity
photocatalysts for applications that are impractical or is often the goal, complete mineralization is unrealistic for the
for which industry lacks interest. To overcome this vast majority of applications.1,82 The resulting incomplete
challenge, researchers need either to overcome the major degradation of hazardous pollutants requires careful assess-
barriers facing traditional applications such as drinking ment of the ecotoxicity83,84 or human toxicity85,86 of the
water and municipal wastewater treatment, or to identify byproducts. The ability of photocatalysis to increase
niche areas, where photocatalytic water treatment can be biodegradability requires further attention with emphasis on
competitive with existing AOPs. the development of methods to enable the rapid assessment of

■
contaminant biodegradability. The higher mineralization
potential of photocatalysis when applied as a polishing step
MOVING AHEAD: DESIGN FOR NICHE for pretreated water can also be advantageous in niche
APPLICATIONS applications where cost and time are less restricted, such as
The need for energy-efficient AOPs will persist, as advances in the treatment of highly turbid waters containing recalcitrant
analytical techniques and increasingly stringent legislation contaminants, space-station water treatment systems,87,88 or
continue to drive lower contaminant minimum concentration the production of ultrapure water for the semiconductor
targets for potable use and environmental discharge. For industry.89
photocatalysis to carve out a place in this growing market, it As a catalytic process, not requiring consumable chemicals is
must be competitive with other AOP technologies, particularly another key benefit of photocatalytic treatment systems. This
UV/H2O2, which is more widely adopted by industry. At pilot- leads to opportunities in applications where transportation of
2942 DOI: 10.1021/acs.est.8b05041
Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

Figure 4. Future Trajectory of Photocatalytic Water Treatment. The development of a new technology can be visualized as following the trace of
the sun on the horizon, rising from its initial conception, then reaching a zenith of popularity before arcing back toward the horizon. Photocatalytic
water treatment has undeniably experienced a peak of academic hype, leading many detractors to espouse the failure of the technology to live up to
its predicted potential. However, it is the opinion of these authors that this need not lead to the sun setting on industrial applications for
photocatalytic water treatment, but that real near-term applications can be achieved considering the maturity of basic science. The practical plateau
of technical performance will likely fall below peak expectations, as with many new innovations; however, valid business models and a clear pathway
for technology transfer to industry can help engineers finally harness the startling benefits of these unique materials.

chemicals is cumbersome (i.e., geographically isolated regions) ability to disinfect and decontaminate water faster than SODIS
or in biological systems that may be sensitive to the addition of alone.93−95 Solar powered applications are intrinsically limited
chemicals. The performance and costs associated with small- by the low-energy density of sunlight (<1000 W/m2); yet
scale groundwater pump and treat systems employing when land area is not restricted and an effective light-
photocatalysis can be comparable to conventional treatment harvesting strategy such as a compound parabolic collector is
technologies,90 while negating the need for a continual supply employed, photocatalysis can be an efficient method for the
of chemicals. Other emerging opportunities include treatment low-energy treatment of small-scale industrial waste
of waste streams from aquaculture and hydroponics, as both streams.96−98 Other solar-based applications have emerged
are often practiced in small scale. Aquaculture waters consist of for industrial off-grid treatment, including floating photo-
a unique set of contaminants including pathogens, taste and catalyst structures in oil sands tailing ponds, which are large in
odor compounds, and antibiotics91 that are not easily treated area and already operate over very long-time scales.99,100 The
with conventional systems. Similarly, photocatalytic treatment use of solar-driven photocatalysis has been suggested as a
of recycled hydroponics water can facilitate the breakdown of possible means of detoxifying treated drinking waters
phytotoxic compounds, leading to increased crop yields containing residual algal toxins, but concerns remain regarding
without leaving a harmful residual.92 cost effectiveness and generation of toxic byproducts.101 At
Perhaps its most greatly espoused attribute is that photo- best, such technology might be utilized for this purpose in
catalysis can be solar powered, making photocatalytic treat- small, remote communities where piped supply is intermittent
and volumes to be treated are small.

■
ment ideal for highly cost-sensitive or energy-restrictive
applications. Regions that lack access to clean water often
lack energy infrastructure, justifying the need for solar- FUTURE OF PHOTOCATALYSIS: SUNRISE OR
powered, household-based, water treatment interventions in SUNSET?
developing regions.7 Several researchers have proposed using Although longer time frames for acceptance of new
TiO2 to enhance solar disinfection (SODIS), demonstrating its technologies in risk-averse industries, such as water treatment,
2943 DOI: 10.1021/acs.est.8b05041
Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

can be expected,102 the more than three decades-long delay in (9) Serpone, N. Relative photonic efficiencies and quantum yields in
technology transfer clearly suggests that photocatalysis for heterogeneous photocatalysis. J. Photochem. Photobiol., A 1997, 104
water treatment is not in the sunrise phase of research and (1), 1−12.
development. However, we do not view it as a sunset, either; (10) Zhang, J.; Nosaka, Y. Quantitative detection of OH radicals for
rather, we see the field overcoming an inflated expectation investigating the reaction mechanism of various visible-light TiO2
photocatalysts in aqueous suspension. J. Phys. Chem. C 2013, 117 (3),
(a.k.a. academic hype),103 exacerbated by its connection to
1383−1391.
concurrent hypes in the fields of materials science and (11) Sun, L.; Bolton, J. R. Determination of the quantum yield for
nanotechnology (Figure 4). While we should not limit our the photochemical generation of hydroxyl radicals in TiO 2
imagination or the boundary of science, it is time for us to suspensions. J. Phys. Chem. 1996, 100 (10), 4127−4134.
reevaluate critically the necessary components of successful (12) Zhang, J.; Nosaka, Y. Mechanism of the OH radical generation
research to move the field of photocatalytic water treatment in photocatalysis with TiO2 of different crystalline types. J. Phys.
forward. Chem. C 2014, 118 (20), 10824−10832.

■
(13) Stafford, U.; Gray, K. A.; Kamat, P. V. Photocatalytic
AUTHOR INFORMATION degradation of 4-chlorophenol: The effects of varying TiO 2
concentration and light wavelength. J. Catal. 1997, 167 (1), 25−32.
Corresponding Author (14) Mills, A.; Morris, S. Photomineralization of 4-chlorophenol
E-mail: [email protected]. Tel: +1-203-432-4386. sensitized by titanium dioxide: a study of the initial kinetics of carbon
ORCID dioxide photogeneration. J. Photochem. Photobiol., A 1993, 71 (1),
75−83.
Pedro J. J. Alvarez: 0000-0002-6725-7199 (15) Lepore, G. P.; Langford, C. H.; Víchová, J.; Vlček, A.
Ezra L. Cates: 0000-0003-0793-0246 Photochemistry and picosecond absorption spectra of aqueous
Wonyong Choi: 0000-0003-1801-9386 suspensions of a polycrystalline titanium dioxide optically transparent
John Crittenden: 0000-0002-9048-7208 in the visible spectrum. J. Photochem. Photobiol., A 1993, 75 (1), 67−
Qilin Li: 0000-0001-5756-3873 75.
(16) Cornu, C. J. G.; Colussi, A. J.; Hoffmann, M. R. Quantum
Xie Quan: 0000-0003-3085-0789 Yields of the photocatalytic oxidation of formate in aqueous TiO2
T. David Waite: 0000-0002-5411-3233 suspensions under continuous and periodic illumination. J. Phys.
Paul Westerhoff: 0000-0002-9241-8759 Chem. B 2001, 105 (7), 1351−1354.
Jae-Hong Kim: 0000-0003-2224-3516 (17) Mierzwa, J. C.; Rodrigues, R.; Teixeira, A. C. S. C., Chapter 2:
Notes UV-hydrogen peroxide processes. In Advanced Oxidation Processes for
Waste Water Treatment; Ameta, R., Ed.; Academic Press, 2018; pp
The authors declare no competing financial interest.

■
13−48.
(18) Liao, C. H.; Gurol, M. D. Chemical oxidation by photolytic
ACKNOWLEDGMENTS decomposition of hydrogen peroxide. Environ. Sci. Technol. 1995, 29
This work was supported by the NSF Nanosystems Engineer- (12), 3007−3014.
(19) Haag, W. R.; Yao, C. C. D. Rate constants for reaction of
ing Research Center for Nanotechnology-Enabled Water hydroxyl radicals with several drinking water contaminants. Environ.
Treatment (NEWT, EEC-1449500). D.L.S.’s contribution Sci. Technol. 1992, 26 (5), 1005−1013.
was supported by the Engineering Research Center for (20) Brame, J.; Long, M.; Li, Q.; Alvarez, P. Inhibitory effect of
Reinventing the Nation’s Urban Water Infrastructure (Re- natural organic matter or other background constituents on
NUWIT, EEC-1028968). photocatalytic advanced oxidation processes: Mechanistic model

■ REFERENCES
(1) Ollis, D. F.; Pelizzetti, E.; Serpone, N. Photocatalyzed
development and validation. Water Res. 2015, 84, 362−371.
(21) Katz, A.; McDonagh, A.; Tijing, L.; Shon, H. K. Fouling and
inactivation of titanium dioxide-based photocatalytic systems. Crit.
Rev. Environ. Sci. Technol. 2015, 45 (17), 1880−1915.
destruction of water contaminants. Environ. Sci. Technol. 1991, 25
(22) Benotti, M. J.; Stanford, B. D.; Wert, E. C.; Snyder, S. A.
(9), 1522−1529.
Evaluation of a photocatalytic reactor membrane pilot system for the
(2) Fujishima, A.; Honda, K. Electrochemical photolysis of water at a
removal of pharmaceuticals and endocrine disrupting compounds
semiconductor electrode. Nature 1972, 238, 37.
(3) Okamoto, K. I.; Yamamoto, Y.; Tanaka, H.; Tanaka, M.; Itaya, A. from water. Water Res. 2009, 43 (6), 1513−1522.
Heterogeneous photocatalytic decomposition of phenol over TiO2 (23) Hurum, D. C.; Agrios, A. G.; Gray, K. A.; Rajh, T.; Thurnauer,
powder. Bull. Chem. Soc. Jpn. 1985, 58 (7), 2015−2022. M. C. Explaining the enhanced photocatalytic activity of Degussa P25
(4) Hoffmann, M. R.; Martin, S. T.; Choi, W. Y.; Bahnemann, D. W. mixed-phase TiO2 Using EPR. J. Phys. Chem. B 2003, 107 (19),
Environmental applications of semiconductor photocatalysis. Chem. 4545−4549.
Rev. 1995, 95 (1), 69−96. (24) Choi, W.; Termin, A.; Hoffmann, M. R. The role of metal ion
(5) Henan Bright Commercial Co., Ltd. Factory sales nano-titanium dopants in quantum-sized TiO2: correlation between photoreactivity
dioxide TiO2 degussa P25. https://www.alibaba.com/product-detail/ and charge carrier recombination dynamics. J. Phys. Chem. 1994, 98
Factory-sales-Nano-Titanium-Dioxide-tio2_60601130450.html?spm= (51), 13669−13679.
a2700.7724838.2017115.1.6d0263f8Q9brPJ (accessed 5/2/2018). (25) Suri, R. P. S.; Liu, J.; Hand, D. W.; Crittenden, J. C.; Perram, D.
(6) Khan, A.; Balakrishnan, K.; Katona, T. Ultraviolet light-emitting L.; Mullins, M. E. Heterogeneous photocatalytic oxidation of
diodes based on group three nitrides. Nat. Photonics 2008, 2, 77. hazardous organic contaminants in water. Water Environ. Res. 1993,
(7) Loeb, S.; Hofmann, R.; Kim, J. H. Beyond the pipeline: 65 (5), 665−673.
Assessing the efficiency limits of advanced technologies for solar water (26) Banerjee, S.; Pillai, S. C.; Falaras, P.; O’Shea, K. E.; Byrne, J. A.;
disinfection. Environ. Sci. Technol. Lett. 2016, 3 (3), 73−80. Dionysiou, D. D. New insights into the mechanism of visible light
(8) Grčić, I.; Li Puma, G. Six-flux absorption-scattering models for photocatalysis. J. Phys. Chem. Lett. 2014, 5 (15), 2543−2554.
photocatalysis under wide-spectrum irradiation sources in annular and (27) Chen, X. B.; Liu, L.; Yu, P. Y.; Mao, S. S. Increasing solar
flat reactors using catalysts with different optical properties. Appl. absorption for photocatalysis with black hydrogenated titanium
Catal., B 2017, 211, 222−234. dioxide nanocrystals. Science 2011, 331 (6018), 746−750.

2944 DOI: 10.1021/acs.est.8b05041

Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

(28) Zhao, C.; Pelaez, M.; Dionysiou, D. D.; Pillai, S. C.; Byrne, J. removal of pharmaceuticals and endocrine disrupting compounds
A.; O’Shea, K. E. UV and visible light activated TiO2 photocatalysis of from water. Water Res. 2009, 43 (6), 1513−1522.
6-hydroxymethyl uracil, a model compound for the potent cyanotoxin (47) Li Puma, G.; Brucato, A. Dimensionless analysis of slurry
cylindrospermopsin. Catal. Today 2014, 224, 70−76. photocatalytic reactors using two-flux and six-flux radiation
(29) Shiraishi, Y.; Sakamoto, H.; Sugano, Y.; Ichikawa, S.; Hirai, T. absorption−scattering models. Catal. Today 2007, 122 (1), 78−90.
Pt−Cu bimetallic alloy nanoparticles supported on anatase TiO2: (48) Ling, L.; Tugaoen, H.; Brame, J.; Sinha, S.; Li, C.; Schoepf, J.;
Highly active catalysts for aerobic oxidation driven by visible light. Hristovski, K.; Kim, J. H.; Shang, C.; Westerhoff, P. Coupling light
ACS Nano 2013, 7 (10), 9287−9297. emitting diodes with photocatalyst-coated optical fibers improves
(30) Chen, C.; Ma, W.; Zhao, J. Semiconductor-mediated quantum yield of pollutant oxidation. Environ. Sci. Technol. 2017, 51
photodegradation of pollutants under visible-light irradiation. Chem. (22), 13319−13326.
Soc. Rev. 2010, 39 (11), 4206−4219. (49) Karches, M.; Morstein, M.; Rudolf von Rohr, P.; Pozzo, R. L.;
(31) Tsukamoto, D.; Shiraishi, Y.; Sugano, Y.; Ichikawa, S.; Tanaka, Giombi, J. L.; Baltanás, M. A. Plasma-CVD-coated glass beads as
S.; Hirai, T. Gold Nanoparticles located at the interface of anatase/ photocatalyst for water decontamination. Catal. Today 2002, 72 (3),
rutile TiO2 particles as active plasmonic photocatalysts for aerobic 267−279.
oxidation. J. Am. Chem. Soc. 2012, 134 (14), 6309−6315. (50) Plesch, G.; Gorbár, M.; Vogt, U. F.; Jesenák, K.; Vargová, M.
(32) Xiong, Z.; Ma, J.; Ng, W. J.; Waite, T. D.; Zhao, X. S. Silver- Reticulated macroporous ceramic foam supported TiO2 for photo-
modified mesoporous TiO2 photocatalyst for water purification. catalytic applications. Mater. Lett. 2009, 63 (3), 461−463.
Water Res. 2011, 45 (5), 2095−2103. (51) Athanasekou, C. P.; Romanos, G. E.; Katsaros, F. K.; Kordatos,
(33) Zhang, Y.; Tang, Z. R.; Fu, X.; Xu, Y. J. TiO2−graphene K.; Likodimos, V.; Falaras, P. Very efficient composite titania
nanocomposites for gas-phase photocatalytic degradation of volatile membranes in hybrid ultrafiltration/photocatalysis water treatment
aromatic pollutant: Is TiO2−graphene truly different from other processes. J. Membr. Sci. 2012, 392−393, 192−203.
TiO2−carbon composite materials? ACS Nano 2010, 4 (12), 7303− (52) Lee, C. G.; Javed, H.; Zhang, D.; Kim, J. H.; Westerhoff, P.; Li,
7314. Q.; Alvarez, P. J. J. Porous electrospun fibers embedding TiO2 for
(34) Liu, Z.; Bai, H.; Sun, D. Facile fabrication of hierarchical porous adsorption and photocatalytic degradation of water pollutants.
TiO2 hollow microspheres with high photocatalytic activity for water Environ. Sci. Technol. 2018, 52 (7), 4285−4293.
purification. Appl. Catal., B 2011, 104 (3), 234−238. (53) Matafonova, G.; Batoev, V. Recent advances in application of
(35) Yu, J. G.; Su, Y. R.; Cheng, B. Template-free fabrication and UV light-emitting diodes for degrading organic pollutants in water
enhanced photocatalytic activity of hierarchical macro-/mesoporous through advanced oxidation processes: A review. Water Res. 2018,
titania. Adv. Funct. Mater. 2007, 17 (12), 1984−1990. 132, 177−189.
(36) Chen, P. C.; Tsai, M. C.; Yang, M. H.; Chen, T. T.; Chen, H. (54) Chen, J.; Loeb, S.; Kim, J. H. LED revolution: fundamentals
C.; Chang, I. C.; Chang, Y. C.; Chen, Y. L.; Lin, I. N.; Chiu, H. T.; and prospects for UV disinfection applications. Environ. Sci.: Water
Lee, C. Y. The “cascade effect” of nano/micro hierarchical structure: Res. Technol. 2017, 3 (2), 188−202.
A new concept for designing the high photoactivity materials − An (55) Dotson, A. D.; Rodriguez, C. E.; Linden, K. G. UV disinfection
example for TiO2. Appl. Catal., B 2013, 142−143, 752−760. implementation status in US water treatment plants. J. - Am. Water
(37) Liu, J.; Liu, Y.; Liu, N.; Han, Y.; Zhang, X.; Huang, H.; Lifshitz, Works Assoc. 2012, 104 (5), E318−E324.
Y.; Lee, S. T.; Zhong, J.; Kang, Z. Metal-free efficient photocatalyst for (56) Grčić, I.; Li Puma, G. Photocatalytic degradation of water
stable visible water splitting via a two-electron pathway. Science 2015, contaminants in multiple photoreactors and evaluation of reaction
347 (6225), 970−974. kinetic constants independent of photon absorption, irradiance,
(38) Niu, P.; Liu, G.; Cheng, H. M. Nitrogen vacancy-promoted reactor geometry, and hydrodynamics. Environ. Sci. Technol. 2013,
photocatalytic activity of graphitic carbon nitride. J. Phys. Chem. C 47 (23), 13702−13711.
2012, 116 (20), 11013−11018. (57) Otálvaro-Marín, H. L.; Mueses, M. A.; Crittenden, J. C.;
(39) Wang, W.; Tade, M. O.; Shao, Z. Research progress of Machuca-Martinez, F. Solar photoreactor design by the photon path
perovskite materials in photocatalysis- and photovoltaics-related length and optimization of the radiant field in a TiO2-based CPC
energy conversion and environmental treatment. Chem. Soc. Rev. reactor. Chem. Eng. J. 2017, 315, 283−295.
2015, 44 (15), 5371−5408. (58) Ahmed, Y. M.; Jongewaard, M.; Li, M.; Blatchley, E. R. Ray
(40) Kim, J.; Lee, C. W.; Choi, W. Platinized WO3 as an tracing for fluence rate simulations in ultraviolet photoreactors.
environmental photocatalyst that generates OH radicals under visible Environ. Sci. Technol. 2018, 52 (8), 4738−4745.
light. Environ. Sci. Technol. 2010, 44 (17), 6849−6854. (59) Barbero, N.; Vione, D. Why dyes should not be used to test the
(41) Pan, C.; Zhu, Y. A review of BiPO4, a highly efficient oxyacid- photocatalytic activity of semiconductor oxides. Environ. Sci. Technol.
type photocatalyst, used for environmental applications. Catal. Sci. 2016, 50 (5), 2130−2131.
Technol. 2015, 5 (6), 3071−3083. (60) Bolton, J. R.; Bircher, K. G.; Tumas, W.; Tolman, C. A. Figures-
(42) Park, H.; Kim, H. I.; Moon, G. H.; Choi, W. Photoinduced of-merit for the technical development and application of advanced
charge transfer processes in solar photocatalysis based on modified oxidation technologies for both electric-and solar-driven systems
TiO2. Energy Environ. Sci. 2016, 9 (2), 411−433. (IUPAC Technical Report). Pure Appl. Chem. 2001, 73, 627.
(43) Pelaez, M.; Nolan, N. T.; Pillai, S. C.; Seery, M. K.; Falaras, P.; (61) Liu, L.; Chen, F.; Yang, F.; Chen, Y.; Crittenden, J.
Kontos, A. G.; Dunlop, P. S. M.; Hamilton, J. W. J.; Byrne, J. A.; Photocatalytic degradation of 2,4-dichlorophenol using nanoscale
O’Shea, K.; Entezari, M. H.; Dionysiou, D. D. A review on the visible Fe/TiO2. Chem. Eng. J. 2012, 181−182, 189−195.
light active titanium dioxide photocatalysts for environmental (62) Xie, R.; Meng, X.; Sun, P.; Niu, J.; Jiang, W.; Bottomley, L.; Li,
applications. Appl. Catal., B 2012, 125, 331−349. D.; Chen, Y.; Crittenden, J. Electrochemical oxidation of ofloxacin
(44) Dong, S.; Feng, J.; Fan, M.; Pi, Y.; Hu, L.; Han, X.; Liu, M.; using a TiO2-based SnO2-Sb/polytetrafluoroethylene resin-PbO2
Sun, J.; Sun, J. Recent developments in heterogeneous photocatalytic electrode: Reaction kinetics and mass transfer impact. Appl. Catal.,
water treatment using visible light-responsive photocatalysts: a review. B 2017, 203, 515−525.
RSC Adv. 2015, 5 (19), 14610−14630. (63) Ryu, J.; Choi, W. Substrate-specific photocatalytic activities of
(45) Van Gerven, T.; Mul, G.; Moulijn, J.; Stankiewicz, A. A review TiO2 and multiactivity test for water treatment application. Environ.
of intensification of photocatalytic processes. Chem. Eng. Process. Sci. Technol. 2008, 42 (1), 294−300.
2007, 46 (9), 781−789. (64) Autin, O.; Hart, J.; Jarvis, P.; MacAdam, J.; Parsons, S. A.;
(46) Benotti, M. J.; Stanford, B. D.; Wert, E. C.; Snyder, S. A. Jefferson, B. Comparison of UV/TiO2 and UV/H2O2 processes in an
Evaluation of a photocatalytic reactor membrane pilot system for the annular photoreactor for removal of micropollutants: Influence of

2945 DOI: 10.1021/acs.est.8b05041

Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

water parameters on metaldehyde removal, quantum yields and (84) Cai, Q.; Hu, J. Decomposition of sulfamethoxazole and
energy consumption. Appl. Catal., B 2013, 138−139, 268−275. trimethoprim by continuous UVA/LED/TiO2 photocatalysis: De-
(65) von Gunten, U. Oxidation processes in water treatment: are we composition pathways, residual antibacterial activity and toxicity. J.
on track? Environ. Sci. Technol. 2018, 52 (9), 5062−5075. Hazard. Mater. 2017, 323, 527−536.
(66) Cates, E. L. Photocatalytic water treatment: So where are we (85) Cantavenera, M. J.; Catanzaro, I.; Loddo, V.; Palmisano, L.;
going with this? Environ. Sci. Technol. 2017, 51 (2), 757−758. Sciandrello, G. Photocatalytic degradation of paraquat and genotox-
(67) Doudrick, K.; Yang, T.; Hristovski, K.; Westerhoff, P. icity of its intermediate products. J. Photochem. Photobiol., A 2007, 185
Photocatalytic nitrate reduction in water: Managing the hole (2), 277−282.
scavenger and reaction by-product selectivity. Appl. Catal., B 2013, (86) Liviac, D.; Creus, A.; Marcos, R. DNA damage induction by
136−137, 40−47. two halogenated acetaldehydes, byproducts of water disinfection.
(68) Testa, J. J.; Grela, M. A.; Litter, M. I. Heterogeneous Water Res. 2010, 44 (8), 2638−2646.
photocatalytic reduction of chromium(VI) over TiO2 particles in (87) Antoniou, M. G.; Dionysiou, D. D. Application of immobilized
the presence of oxalate: Involvement of Cr(V) species. Environ. Sci. titanium dioxide photocatalysts for the degradation of creatinine and
Technol. 2004, 38 (5), 1589−1594. phenol, model organic contaminants found in NASA’s spacecrafts
(69) Prairie, M. R.; Evans, L. R.; Stange, B. M.; Martinez, S. L. An wastewater streams. Catal. Today 2007, 124 (3), 215−223.
investigation of titanium dioxide photocatalysis for the treatment of (88) Liu, X.; Chen, M.; Bian, Z.; Liu, C. C. Studies on urine
water contaminated with metals and organic chemicals. Environ. Sci. treatment by biological purification using Azolla and UV photo-
Technol. 1993, 27 (9), 1776−1782. catalytic oxidation. Adv. Space Res. 2008, 41 (5), 783−786.
(70) Cheng, Q.; Wang, C.; Doudrick, K.; Chan, C. K. Hexavalent (89) Degenova, J.; Shadman, F. Recovery, reuse, and recycle of water
chromium removal using metal oxide photocatalysts. Appl. Catal., B in semiconductor wafer fabrication facilities. Environ. Prog. 1997, 16
2015, 176−177, 740−748. (4), 263−267.
(71) Marks, R.; Yang, T.; Westerhoff, P.; Doudrick, K. Comparative (90) Turchi, C. S.; Mehos, M. S.; Link, H. F. Design and Cost of Solar
analysis of the photocatalytic reduction of drinking water oxoanions Photocatalytic Systems for Groundwater Remediation; U.S. Department
using titanium dioxide. Water Res. 2016, 104, 11−19. of Energy Office of Scientific and Technical Information, 1992.
(72) Choi, Y.; Koo, M. S.; Bokare, A. D.; Kim, D. H.; Bahnemann, DOI: 10.2172/1114050.
D. W.; Choi, W. Sequential process combination of photocatalytic (91) Bian, Z.; Cao, F.; Zhu, J.; Li, H. Plant pptake-assisted round-
oxidation and dark reduction for the removal of organic pollutants the-clock photocatalysis for complete purification of aquaculture
and Cr(VI) using Ag/TiO2. Environ. Sci. Technol. 2017, 51 (7), wastewater using sunlight. Environ. Sci. Technol. 2015, 49 (4), 2418−
3973−3981. 2424.
(73) Kim, H. I.; Choi, Y.; Hu, S.; Choi, W.; Kim, J. H. Photocatalytic (92) Sunada, K.; Ding, X. G.; Utami, M. S.; Kawashima, Y.; Miyama,
hydrogen peroxide production by anthraquinone-augmented poly- Y.; Hashimoto, K. Detoxification of phytotoxic compounds by TiO2
photocatalysis in a recycling hydroponic cultivation system of
meric carbon nitride. Appl. Catal., B 2018, 229, 121−129.
(74) Liu, Y.; Yao, W.; Liu, D.; Zong, R.; Zhang, M.; Ma, X.; Zhu, Y. asparagus. J. Agric. Food Chem. 2008, 56 (12), 4819−4824.
(93) Byrne, J. A.; Fernandez-Ibanez, P. A.; Dunlop, P. S. M.;
Enhancement of visible light mineralization ability and photocatalytic
Alrousan, D. M. A.; Hamilton, J. W. J. Photocatalytic enhancement for
activity of BiPO4/BiOI. Appl. Catal., B 2015, 163, 547−553.
solar disinfection of water: A review. Int. J. Photoenergy 2011, 2011,
(75) Kansal, S. K.; Singh, M.; Sud, D. Studies on TiO2/ZnO
1−12.
photocatalysed degradation of lignin. J. Hazard. Mater. 2008, 153 (1),
(94) Malato, S.; Fernandez-Ibanez, P.; Maldonado, M. I.; Blanco, J.;
412−417.
Gernjak, W. Decontamination and disinfection of water by solar
(76) Pekakis, P. A.; Xekoukoulotakis, N. P.; Mantzavinos, D.
photocatalysis: Recent overview and trends. Catal. Today 2009, 147
Treatment of textile dyehouse wastewater by TiO2 photocatalysis.
(1), 1−59.
Water Res. 2006, 40 (6), 1276−1286. (95) Alrousan, D. M. A.; Dunlop, P. S. M.; McMurray, T. A.; Byrne,
(77) Sahu, S. P.; Qanbarzadeh, M.; Ateia, M.; Torkzadeh, H.; J. A. Photocatalytic inactivation of E. coli in surface water using
Maroli, A. S.; Cates, E. L. Rapid degradation and mineralization of immobilised nanoparticle TiO2 films. Water Res. 2009, 43 (1), 47−54.
perfluorooctanoic acid by a new petitjeanite Bi3O(OH)(PO4)2 (96) Spasiano, D.; Marotta, R.; Malato, S.; Fernandez-Ibañez, P.; Di
microparticle ultraviolet photocatalyst. Environ. Sci. Technol. Lett. Somma, I. Solar photocatalysis: materials, reactors, some commercial,
2018, 5 (8), 533−538. and pre-industrialized applications. A comprehensive approach. Appl.
(78) Xu, B.; Ahmed, M. B.; Zhou, J. L.; Altaee, A.; Wu, M.; Xu, G. Catal., B 2015, 170−171, 90−123.
Photocatalytic removal of perfluoroalkyl substances from water and (97) Feitz, A. J.; Boyden, B. H.; Waite, T. D. Evaluation of two solar
wastewater: Mechanism, kinetics and controlling factors. Chemosphere pilot scale fixed-bed photocatalytic reactors. Water Res. 2000, 34 (16),
2017, 189, 717−729. 3927−3932.
(79) Oller, I.; Gernjak, W.; Maldonado, M. I.; Pérez-Estrada, L. A.; (98) Colina-Márquez, J.; Machuca-Martínez, F.; Li Puma, G.
Sánchez-Pérez, J. A.; Malato, S. Solar photocatalytic degradation of Photocatalytic mineralization of commercial herbicides in a pilot-
some hazardous water-soluble pesticides at pilot-plant scale. J. Hazard. scale solar CPC reactor: Photoreactor modeling and reaction kinetics
Mater. 2006, 138 (3), 507−517. constants independent of radiation field. Environ. Sci. Technol. 2009,
(80) Konstantinou, I. K.; Albanis, T. A. Photocatalytic trans- 43 (23), 8953−8960.
formation of pesticides in aqueous titanium dioxide suspensions using (99) McQueen, A. D.; Hendrikse, M.; Gaspari, D. P.; Kinley, C. M.;
artificial and solar light: intermediates and degradation pathways. Rodgers, J. H.; Castle, J. W. Performance of a hybrid pilot-scale
Appl. Catal., B 2003, 42 (4), 319−335. constructed wetland system for treating oil sands process-affected
(81) Minero, C.; Pelizzetti, E.; Malato, S.; Blanco, J. Large solar water from the Athabasca oil sands. Ecol. Eng. 2017, 102, 152−165.
plant photocatalytic water decontamination: Degradation of atrazine. (100) Leshuk, T.; Krishnakumar, H.; de Oliveira Livera, D.; Gu, F.
Sol. Energy 1996, 56 (5), 411−419. Floating photocatalysts for passive solar degradation of naphthenic
(82) Chong, M. N.; Jin, B.; Chow, C. W. K.; Saint, C. Recent acids in oil sands process-affected water. Water 2018, 10 (2), 202.
developments in photocatalytic water treatment technology: A review. (101) Feitz, A. J.; Waite, T. D.; Jones, G. J.; Boyden, B. H.; Orr, P. T.
Water Res. 2010, 44 (10), 2997−3027. Photocatalytic degradation of the blue green algal toxin microcystin-
(83) Malato, S.; Cáceres, J.; Fernández-Alba, A. R.; Piedra, L.; LR in a natural organic-aqueous matrix. Environ. Sci. Technol. 1999, 33
Hernando, M. D.; Agüera, A.; Vial, J. Photocatalytic treatment of (2), 243−249.
diuron by solar photocatalysis: Evaluation of main intermediates and (102) Kiparsky, M.; Sedlak, D. L.; Thompson, B. H., J.; Truffer, B.
toxicity. Environ. Sci. Technol. 2003, 37 (11), 2516−2524. The innovation deficit in urban water: The need for an integrated

2946 DOI: 10.1021/acs.est.8b05041

Environ. Sci. Technol. 2019, 53, 2937−2947
Environmental Science & Technology Feature

perspective on institutions, organizations, and technology. Environ.

Eng. Sci. 2013, 30 (8), 395−408.
(103) van Lente, H.; Spitters, C.; Peine, A. Comparing technological
hype cycles: Towards a theory. Technol. Forecast. Soc. Change 2013, 80
(8), 1615−1628.

2947 DOI: 10.1021/acs.est.8b05041

Environ. Sci. Technol. 2019, 53, 2937−2947