The current rapid industrial development causes the serious energy and environmental crises. Photocatalyts provide a potential strategy to solve these problems because these materials not only can directly convert solar energy into usable or storable energy resources but also can decompose organic pollutants under solar-light irradiation. However, the aforementioned applications require photocatalysts with a wide absorption range, long-term stability, high charge-separation efficiency and strong redox ability. Unfortunately, it is often difficult for a single-component photocatalyst to simultaneously fulfill all these requirements. The artificial heterogeneous Z-scheme photocatalytic systems, mimicking the natural photosynthesis process, overcome the drawbacks of single-component photocatalysts and satisfy those aforementioned requirements. Such multi-task systems have been extensively investigated in the past decade. Especially, the all-solid-state Z-scheme photocatalytic systems without redox pair have been widely used in the water splitting, solar cells, degradation of pollutants and CO2 conversion, which have a huge potential to solve the current energy and environmental crises facing the modern industrial development. Thus, this review gives a concise overview of the all-solid-state Z-scheme photocatalytic systems, including their composition, construction, optimization and applications.

All-Solid-State Z-Scheme Photocatalytic Systems

Solar-driven water splitting provides a leading approach to store the abundant yet intermittent solar energy and produce hydrogen as a clean and sustainable energy carrier. A straightforward route to light-driven water splitting is to apply self-supported particulate photocatalysts, which is expected to allow solar hydrogen to be competitive with fossil-fuel-derived hydrogen on a levelized cost basis. More importantly, the powder-based systems can lend themselves to making functional panels on a large scale while retaining the intrinsic activity of the photocatalyst. However, all attempts to generate hydrogen via powder-based solar water-splitting systems to date have unfortunately fallen short of the efficiency values required for practical applications. Photocatalysis on photocatalyst particles involves three sequential steps: (i) absorption of photons with higher energies than the bandgap of the photocatalysts, leading to the excitation of electron-hole pairs in the particles, (ii) charge separation and migration of these photoexcited carriers, and (iii) surface chemical reactions based on these carriers. In this review, we focus on the challenges of each step and summarize material design strategies to overcome the obstacles and limitations. This review illustrates that it is possible to employ the fundamental principles underlying photosynthesis and the tools of chemical and materials science to design and prepare photocatalysts for overall water splitting.

Particulate Photocatalysts for Light-Driven Water Splitting: Mechanisms, Challenges, and Design Strategies

Overall water splitting using powdered photocatalysts is a promising approach to large-scale solar hydrogen production. This Review details recent developments in particulate photocatalysts for overall water splitting based on one- and two-step photoexcitation systems.

Particulate photocatalysts for overall water splitting

Charge kinetics is highly critical in determining the quantum efficiency of solar-to-chemical conversion in photocatalysis, and this includes, but is not limited to, the separation of photoexcited electron–hole pairs, utilization of plasmonic hot carriers and delivery of photo-induced charges to reaction sites, as well as activation of reactants by energized charges. In this review, we highlight the recent progress on probing and steering charge kinetics toward designing highly efficient photocatalysts and elucidate the fundamentals behind the combinative use of controlled synthesis, characterization techniques (with a focus on spectroscopic characterizations) and theoretical simulations in photocatalysis studies. We first introduce the principles of various processes associated with charge kinetics that account for or may affect photocatalysis, from which a set of parameters that are critical to photocatalyst design can be summarized. We then outline the design rules for photocatalyst structures and their corresponding synthetic approaches. The implementation of characterization techniques and theoretical simulations in different steps of photocatalysis, together with the associated fundamentals and working mechanisms, are also presented. Finally, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields.

Steering charge kinetics in photocatalysis: intersection of materials syntheses, characterization techniques and theoretical simulations

Semiconductor nanowires (NWs) have been studied extensively for over two decades for their novel electronic, photonic, thermal, electrochemical and mechanical properties. This comprehensive review article summarizes major advances in the synthesis, characterization, and application of these materials in the past decade. Developments in the understanding of the fundamental principles of "bottom-up" growth mechanisms are presented, with an emphasis on rational control of the morphology, stoichiometry, and crystal structure of the materials. This is followed by a discussion of the application of nanowires in i) electronic, ii) sensor, iii) photonic, iv) thermoelectric, v) photovoltaic, vi) photoelectrochemical, vii) battery, viii) mechanical, and ix) biological applications. Throughout the discussion, a detailed explanation of the unique properties associated with the one-dimensional nanowire geometry will be presented, and the benefits of these properties for the various applications will be highlighted. The review concludes with a brief perspective on future research directions, and remaining barriers which must be overcome for the successful commercial application of these technologies.

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25th Anniversary Article: Semiconductor Nanowires – Synthesis, Characterization, and Applications

We report on the achievement of wafer-level photocatalytic overall water splitting on GaN nanowires grown by molecular beam epitaxy with the incorporation of Rh/Cr2O3 core–shell nanostructures acting as cocatalysts, through which H2 evolution is promoted by the noble metal core (Rh) while the water forming back reaction over Rh is effectively prevented by the Cr2O3 shell O2 diffusion barrier. The decomposition of pure water into H2 and O2 by GaN nanowires is confirmed to be a highly stable photocatalytic process, with the turnover number per unit time well exceeding the value of any previously reported GaN powder samples.

Wafer-level photocatalytic water splitting on gan nanowire arrays grown by molecular beam epitaxy

The conversion of solar energy into hydrogen via water splitting process is one of the key sustainable technologies for future clean, storable, and renewable source of energy. Therefore, development of visible light-responsive and efficient photocatalyst material has been of immense interest, but with limited success. Here, we show that overall water splitting under visible-light irradiation can be achieved using a single photocatalyst material. Multiband InGaN/GaN nanowire heterostructures, decorated with rhodium (Rh)/chromium-oxide (Cr2O3) core–shell nanoparticles can lead to stable hydrogen production from pure (pH ∼ 7.0) water splitting under ultraviolet, blue and green-light irradiation (up to ∼560 nm), the longest wavelength ever reported. At ∼440–450 nm wavelengths, the internal quantum efficiency is estimated to be ∼13%, the highest value reported in the visible spectrum. The turnover number under visible light well exceeds 73 in 12 h. Detailed analysis further confirms the stable photocatalytic a...

One-Step Overall Water Splitting under Visible Light Using Multiband InGaN/GaN Nanowire Heterostructures

Ultra-compact waveguide electroabsorption optical switches and photodetectors with micron- and sub-micron lengths and compatible with silicon (Si) waveguides are demonstrated using the insulator-metal phase transition of vanadium dioxide (VO(2)). A 1 μm long hybrid Si-VO(2) device is shown to achieve a high extinction ratio of 12 dB and a competitive insertion loss of 5 dB over a broad bandwidth of 100 nm near λ = 1550 nm. The device, operated as a photodetector, can measure optical powers less than 1 μW with a responsivity in excess of 10 A/W. With volumes that are about 100 to 1000 times smaller than today's active Si photonic components, the hybrid Si-VO(2) devices show the feasibility of integrating transition metal oxides on Si photonic platforms for nanoscale electro-optic elements.

Wavelength-size hybrid Si-VO(2) waveguide electroabsorption optical switches and photodetectors.

Surface plasmon polaritons can substantially reduce the sizes of optical devices, since they can concentrate light to (sub)wavelength scales. However, (sub)wavelength-scale electro-optic plasmonic switches or modulators with high efficiency, low insertion loss, and high extinction ratios remain a challenge due to their small active volumes. Here, we use the insulator-metal phase transition of a correlated-electron material, vanadium dioxide, to overcome this limitation and demonstrate compact, broadband, and efficient plasmonic switches with integrated electrical control. The devices are micron-scale in length and operate near a wavelength of 1550 nm. The switching bandwidths exceed 100 nm and applied voltages of only 400 mV are sufficient to attain extinction ratios in excess of 20 dB. Our results illustrate the potential of using phase transition materials for highly efficient and ultra-compact plasmonic switches and modulators.

Low-voltage broadband hybrid plasmonic-vanadium dioxide switches

The insulator-metal phase transition of a correlated-electron material, vanadium dioxide, is used to demonstrate electrically controlled, compact, broadband, and low voltage plasmonic switches. The devices are micron-scale in length and operate near a wavelength of 1550 nm. The switching bandwidths exceed 100 nm and 400 mV is sufficient to attain extinction ratios in excess of 20 dB. The results illustrate the promise of using phase transition materials for efficient and ultra-compact plasmonic switches and modulators.

Suzanne Paradis

Papers

Wafer-level photocatalytic water splitting on gan nanowire arrays grown by molecular beam epitaxy

One-Step Overall Water Splitting under Visible Light Using Multiband InGaN/GaN Nanowire Heterostructures

Wavelength-size hybrid Si-VO(2) waveguide electroabsorption optical switches and photodetectors.

Low-voltage broadband hybrid plasmonic-vanadium dioxide switches

Sub-volt broadband hybrid plasmonic-vanadium dioxide switches