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Lab on a Chip Lab on a Chip View Article Online FOCUS View Journal | View Issue Nano-photocatalysts in microfluidics, energy conversion and environmental applications Cite this: Lab Chip,2015,15,2352 Jemish Parmar,a Seungwook Jang,b Lluís Soler,c Dong-Pyo Kimb and Samuel Sánchez*ade Extensive studies have been carried out on photocatalytic materials in recent years as photocatalytic reactions offer a promising solution for solar energy conversion and environmental remediation. Currently available commercial photocatalysts still lack efficiency and thus are economically not viable for replacing traditional sources of energy. This article focuses on recent developments in novel nano-photocatalyst DOI: 10.1039/c5lc90047f materials to enhance photocatalytic activity. Recent reports on optofluidic systems, new synthesis of www.rsc.org/loc photocatalytic composite materials and motile photocatalysts are discussed in this article. The development of microfluidic reactors for photocatalytic Development of novel photocatalysts and screening of the Creative Commons Attribution-NonCommercial 3.0 Unported Licence. applications presents valuable advantages like simultaneous optimal conditions to study mechanisms and kinetics is chal- and fine control of light and fluids, large surface area-to- lenging due to expensive and bulky setup. Conventional volume ratio and uniform distribution of light onto the experiments typically require large scale volume setups with photocatalyst. Several groups have used microfluidic chips for enhanced chemical reaction performance.1 The synergy of combining optofluidics and photocatalysis could boost photo- catalytic reaction rates and yields, due to an improvement of the mass and photon transfer in the microfluidic reactors.2 Recent research with non-titania based novel active nano- This article is licensed under a photocatalysts and titania based novel photocatalytic systems are discussed in this article. The employment of novel nano- photocatalysts is a promising approach for the development Open Access Article. Published on 22 April 2015. Downloaded 16/11/2016 14:04:22. of photocatalytic reactors for multiple applications such as solar energy conversion and photodegradation of organics. We expect the field of nano-photocatalytic systems will grow substantially in the near future. Microfluidics Optofluidics, which combines microfluidics and optics has become a promising platform for photocatalytic reactions due to short light travel distance within the microchannels. Optofluidic systems increase photocatalytic reaction rate because of the improved mass and photon transfer efficiency. a Max-Planck Institute for Intelligent Systems, Heisenbergstr. 3, 70569 Stuttgart, Germany. E-mail: [email protected], [email protected] b National Center of Applied Microfluidic Chemistry, Department of Chemical Engineering, POSTECH (Pohang University of Science and Technology), Pohang, Korea 790-784 c Institute of Energy Technologies, Universitat Politècnica de Catalunya, Diagonal 647, 08028 Barcelona, Catalonia, Spain Fig. 1 Various types of optofluidic microreactors. (A) Scheme and d Institute for Bioengineering of Catalonia (IBEC), Baldiri I Reixac 10-12, 08028 photograph of thin TiO2 film coated planar microreactor. (B) Scheme Barcelona, Spain of nanofibrous TiO2 microreactor. (C) Schemes and working principle e Institució Catalana de Recerca i Estudis Avançats (ICREA), Psg. Lluís Companys, of μ-PFC microreactor. Reprinted from ref. 3 (A), ref. 4 (B) and ref. 5 23, 08010 Barcelona, Spain (C) with permission. 2352 | Lab Chip,2015,15, 2352–2356 This journal is © The Royal Society of Chemistry 2015 View Article Online Lab on a Chip Focus catalysts containing precious metals. Miniaturized reactor dimensional ordered assembly of thin-shell Au/TiO2 hollow space in a microreactor can minimize labour force, cost of nanospheres (Au/TiO2 3DHNSs) that showed higher photo- experiment and allow for rapid optimization of reactions. catalytic activity under visible light than conventional Au/ Ahsan et al. used a microfluidic platform to study the kinet- TiO2 nanopowders. The authors also investigated the optical 3 ics of photocatalytic water-splitting. They used a planar type and photocatalytic properties of the Au/TiO2 3DHNSs struc- PDMS reactor with glass to maximize the light exposure area ture. Analyzing the reflection and absorption spectra of the – – (Fig. 1A). Pt TiO2 photocatalyst was synthesized by sol gel samples, the authors concluded that the particular architec- reaction and the prepared colloidal suspension was spread ture of the photocatalyst plays a key role in enhancement of on the glass substrate. O2 and H2 were evolved by Z-scheme visible light absorption. The wavelength overlapping between system with redox mediators. The reaction rates for O2 and surface plasmon resonance of Au NPs at 580 nm and the – H2 were measured under different flow rates and concentra- photonic stop band in the range 550 620 nm (Fig. 2A) pro- tions of mediator. It was observed that the reaction efficiency duces an enhanced light harvesting effect. It is known that was clearly improved with increasing flow rate due to photons with wavelengths near to the stop band edges can be enhanced mass transport. Especially higher flow rates would slowed down and propagate in the material with strong low yield 2-fold improved reaction rates. group velocities through an effect called the slow photon Meng et al. reported a novel microfluidic-based photocata- effect.7 When the wavelength of the slow photon overlaps lytic microreactor by using nanofibrous TiO2 as a photo- catalyst with a simple fabrication process and high photo- 4 catalytic efficiency. The nanofibrous TiO2 catalyst was produced by electrospinning and calcination process with − high BET surface area (20.8 m2 g 1). The prepared nano- fibrous TiO2 was transferred and sealed between a PDMS Creative Commons Attribution-NonCommercial 3.0 Unported Licence. mold and glass substrate (Fig. 1B). The photocatalytic activity of the nanofibrous TiO2 microreactor was compared with the TiO2 film microreactor by measuring methylene blue (MB) photodegradation. The investigation of photocatalytic activity with different flow rates revealed that the MB degradation reaction rate was increased sharply with an increase in resi- dence time. The highly porous structure of nanofibrous TiO2 provides a large surface area while the TiO2 film reactor only provides limited contact area. The nanofibrous TiO2 micro- This article is licensed under a reactor has a higher efficiency of photocatalytic reaction than that of bulk and film microreactors. Li et al. proposed a micro-photocatalytic fuel cell (μ-PFC) Open Access Article. Published on 22 April 2015. Downloaded 16/11/2016 14:04:22. with membrane-free and air-breathing modes.5 As shown in Fig. 1C, the μ-PFC was designed by fabricating PDMS and a carbon paper with Pt on the TiO2 film deposited FTO glass. As compared to traditional PFCs, μ-PFCs with a shorter dis- tance between the electrodes along with the membrane can decrease the mass/photon transfer resistance, resulting in enhanced electricity generation. Furthermore, the air- breathing cathode can supply O2 from the surrounding air with intrinsic large surface to volume ratio, which provides a simple and compact structure as compared to conventional Fig. 2 (A) Diffuse reflectance UV-vis spectra for Au/TiO 3DHNSs and μ 2 PFCs. The -PFCs achieved high performance with 0.58 mW TiO2 3DHNSs as a reference sample. The shaded area in (A) illustrates −2 cm of maximum power density and a degradation efficiency the presence of the photonic stop band. (B) Generation of CO2 under λ ≥ of 83.9%. This new type of μ-PFC brings in the possibility of visible light illumination ( 420 nm) for 10 h using (1) Au/TiO2-P25, promising applications like degrading pollutants and gener- (2) Au/TiO2 3DHNSs, (3) crushed Au/TiO2 3DHNSs, (4) Au/TiO2-HNSs (without the 3D ordered structure) as photocatalysts. (C) Photocata- ating electricity. lytic degradation of methyl orange (MO) solution in the presence of WS2 nanosheets under UV, visible and NIR light irradiation. (D) Sche- matic of the CO2 photoreduction to CO using CuIJII) nanoclusters − Energy conversion and environmental grafted onto Nb3O8 nanosheets. (E) Schematic of the CO2 photore- duction to formic acid using a Ru complex/C3N4 hybrid photocatalyst. applications CB and VB stand for conduction band and valence band, respectively. (F) Photocatalytic, photothermal and electron shuttling effect in the Dinh et al. described a visible light activated photocatalyst nanocomposite of P25 attached rGO. Reprinted from ref. 6 (A, B), ref. 6 based on nanostructured Au/TiO2. They fabricated a three- 8 (C), ref. 9 (D), ref. 10 (E) and ref. 11 (F) with permission. This journal is © The Royal Society of Chemistry 2015 Lab Chip,2015,15, 2352–2356 | 2353 View Article Online Focus Lab on a Chip with the specific absorption of the material, the enhance- bands, respectively. The generated electrons are injected into ment of the absorption can occur as a result of increased the Ru complex, which hosts the active site for CO2 reduc- interaction between slow photons and the material. Their tion. Therefore, the photocatalytic efficiency of the present results showed that, besides the slow photon effect, the mul- system depends on the structure of the Ru complex. The tiple light scattering caused by the Au/TiO2 3DHNSs is also experimental results testing different Ru complexes on the important for the enhancement
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