Engineered inverse opal structured semiconductors for solar light-driven environmental catalysis

Gao, Junxian; Tian, Wenjie; Zhang, Huayang; Wang, Shaobin

doi:10.1039/d2nr03924a

Cited by 11 publications

(3 citation statements)

References 221 publications

(235 reference statements)

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“…We refer readers to recent reviews − that comprehensively evaluate these structures for heterogeneous catalysis. Moreover, while we center our discussions around colloidal templating in catalyst design for thermocatalysis, we acknowledge the closely related application of colloidal templating in photo-, electro-, and photoelectro-catalyst/electrode design and likewise refer readers to these complementary reviews. − …”

Section: Introductionmentioning

confidence: 99%

Colloidal Templating in Catalyst Design for Thermocatalysis

Lim,

Aizenberg,

Aizenberg

2024

J. Am. Chem. Soc.

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Conventional catalyst preparative methods commonly entail the impregnation, precipitation, and/or immobilization of nanoparticles on their supports. While convenient, such methods do not readily afford the ability to control collective ensemblelike nanoparticle properties, such as nanoparticle proximity, placement, and compartmentalization. In this Perspective, we illustrate how incorporating colloidal templating into catalyst design for thermocatalysis confers synthetic advantages to facilitate new catalytic investigations and augment catalytic performance, focusing on three colloid-templated catalyst structures: 3D macroporous structures, hierarchical macro-mesoporous structures, and discrete hollow nanoreactors. We outline how colloidal templating decouples the nanoparticle and support formation steps to devise modular catalyst platforms that can be flexibly tuned at different length scales. Of particular interest is the raspberry colloid templating (RCT) method which confers high thermomechanical stability by partially embedding nanoparticles within its support, while retaining high levels of reactant accessibility. We illustrate how the high modularity of the RCT approach allows one to independently control collective nanoparticle properties, such as nanoparticle proximity and localization, without concomitant changes to other catalytic descriptors that would otherwise confound analyses of their catalytic performance. We next discuss how colloidal templating can be employed to achieve spatially disparate active site functionalization while directing reactant transport within the catalyst structure to enhance selectivity in multistep catalytic cascades. Throughout this Perspective, we highlight developments in advanced characterization that interrogate transport phenomena and/or derive new insights into these catalyst structures. Finally, we offer our outlook on the future roles, applications, and challenges of colloidal templating in catalyst design for thermocatalysis.

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Section: Introductionmentioning

confidence: 99%

Colloidal Templating in Catalyst Design for Thermocatalysis

Lim,

Aizenberg,

Aizenberg

2024

J. Am. Chem. Soc.

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“…[24,25] In particular, inverse opals (IOs) and nanobowl (NB) arrays, which exhibit favorable properties for photoanodes, can be readily prepared by templating three-dimensional and two-dimensional colloidal crystals, respectively. [26][27][28] For example, hierarchical nanorod@NB array photoanodes prepared by nanosphere lithography achieved significantly enhanced PEC performance for the TiO 2 [29] and Fe 2 O 3 [30] systems. As expected, considerable efforts have been devoted to the colloidal crystal-templated BiVO 4 photoanodes.…”

Section: Introductionmentioning

confidence: 99%

Dual Heterojunctions and Nanobowl Morphology Engineered BiVO₄ Photoanodes for Enhanced Solar Water Splitting

Ren,

Zhou,

et al. 2023

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Photoelectrochemical (PEC) water splitting represents an attractive strategy to realize the conversion from solar energy to hydrogen energy, but severe charge recombination in photoanodes significantly limits the conversion efficiency. Herein, a unique BiVO4 (BVO) nanobowl (NB) heterojunction photoanode, which consists of [001]‐oriented BiOCl underlayer and BVO nanobowls containing embedded BiOCl nanocrystals, is fabricated by nanosphere lithography followed by in situ transformation. Experimental characterizations and theoretical simulation prove that nanobowl morphology can effectively enhance light absorption while reducing carrier diffusion path. Density functional theory (DFT) calculations show the tendency of electron transfer from BVO to BiOCl. The [001]‐oriented BiOCl underlayer forms a compact type II heterojunction with the BVO, favoring electron transfer from BVO through BiOCl to the substrate. Furthermore, the embedded BiOCl nanoparticles form a bulk heterojunction to facilitate bulk electron transfer. Consequently, the dual heterojunctions engineered BVO/BiOCl NB photoanode exhibits attractive PEC performance toward water oxidation with an excellent bulk charge separation efficiency of 95.5%, and a remarkable photocurrent density of 3.38 mA cm−2 at 1.23 V versus reversible hydrogen electrode, a fourfold enhancement compared to the flat BVO counterpart. This work highlights the great potential of integrating dual heterojunctions engineering and morphology engineering in fabricating high‐performance photoelectrodes toward efficient solar conversion.

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“…In recent years, different approaches have been developed to reduce the harmful effect of trace organic chemicals from natural waters. Promising results and progress for semiconductor oxide inverse opals (IOs) in water purification processes have been frequently reported [5,6]. IOs are photonic crystals of a highly ordered three-dimensionally interconnected microporous skeleton accompanied by a high specific surface area and unique optical characteristics, such as the optical band gap [7], photo localization [8,9], negative refractive index [10], slow light effect [11,12], and super prism effect [13], for various applications such as photocatalysis [14,15], gas sensors [16], and energy storage [17,18].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of TiO2/Al2O3 Double-Layer Inverse Opal by Thermal and Plasma-Assisted Atomic Layer Deposition for Photocatalytic Applications

et al. 2023

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In comparison to conventional nano-infiltration approaches, the atomic layer deposition (ALD) technology exhibits greater potential in the fabrication of inverse opals (IOs) for photocatalysts. In this study, TiO2 IO and ultra-thin films of Al2O3 on IO were successfully deposited using thermal or plasma-assisted ALD and vertical layer deposition from a polystyrene (PS) opal template. SEM/EDX, XRD, Raman, TG/DTG/DTA-MS, PL spectroscopy, and UV Vis spectroscopy were used for the characterization of the nanocomposites. The results showed that the highly ordered opal crystal microstructure had a face-centered cubic (FCC) orientation. The proposed annealing temperature efficiently removed the template, leaving the anatase phase IO, which provided a small contraction in the spheres. In comparison to TiO2/Al2O3 plasma ALD, TiO2/Al2O3 thermal ALD has a better interfacial charge interaction of photoexcited electron–hole pairs in the valence band hole to restrain recombination, resulting in a broad spectrum with a peak in the green region. This was demonstrated by PL. Strong absorption bands were also found in the UV regions, including increased absorption due to slow photons and a narrow optical band gap in the visible region. The results from the photocatalytic activity of the samples show decolorization rates of 35.4%, 24.7%, and 14.8%, for TiO2, TiO2/Al2O3 thermal, and TiO2/Al2O3 plasma IO ALD samples, respectively. Our results showed that ultra-thin amorphous ALD-grown Al2O3 layers have considerable photocatalytic activity. The Al2O3 thin film grown by thermal ALD has a more ordered structure compared to the one prepared by plasma ALD, which explains its higher photocatalytic activity. The declined photocatalytic activity of the combined layers was observed due to the reduced electron tunneling effect resulting from the thinness of Al2O3.

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Engineered inverse opal structured semiconductors for solar light-driven environmental catalysis

Abstract: Inverse opal (IO) macroporous semiconductor materials with unique physicochemical advantages have been widely used in solar-related environmental areas. In this minireview, we first summarize the synthetic methods of IO materials,...

Cited by 11 publications

References 221 publications

Colloidal Templating in Catalyst Design for Thermocatalysis

Colloidal Templating in Catalyst Design for Thermocatalysis

Dual Heterojunctions and Nanobowl Morphology Engineered BiVO₄ Photoanodes for Enhanced Solar Water Splitting

Synthesis of TiO2/Al2O3 Double-Layer Inverse Opal by Thermal and Plasma-Assisted Atomic Layer Deposition for Photocatalytic Applications

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Engineered inverse opal structured semiconductors for solar light-driven environmental catalysis

Abstract: Inverse opal (IO) macroporous semiconductor materials with unique physicochemical advantages have been widely used in solar-related environmental areas. In this minireview, we first summarize the synthetic methods of IO materials,...

Cited by 11 publications

References 221 publications

Colloidal Templating in Catalyst Design for Thermocatalysis

Colloidal Templating in Catalyst Design for Thermocatalysis

Dual Heterojunctions and Nanobowl Morphology Engineered BiVO4 Photoanodes for Enhanced Solar Water Splitting

Synthesis of TiO2/Al2O3 Double-Layer Inverse Opal by Thermal and Plasma-Assisted Atomic Layer Deposition for Photocatalytic Applications

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Dual Heterojunctions and Nanobowl Morphology Engineered BiVO₄ Photoanodes for Enhanced Solar Water Splitting