Maochang Liu

On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystals

Controlling the shape or morphology of metal nanocrystals is central to the realization of their many applications in catalysis, plasmonics, and electronics. In one of the approaches, the metal nanocrystals are grown from seeds of certain crystallinity through the addition of atomic species. In this case, manipulating the rates at which the atomic species are added onto different crystallographic planes of a seed has been actively explored to control the growth pattern of a seed and thereby the shape or morphology taken by the final product. Upon deposition, however, the adsorbed atoms (adatoms) may not stay at the same sites where the depositions occur. Instead, they can migrate to other sites on the seed owing to the involvement of surface diffusion, and this could lead to unexpected deviations from a desired growth pathway. Herein, we demonstrated that the growth pathway of a seed is indeed determined by the ratio between the rates for atom deposition and surface diffusion. Our result suggests that surface diffusion needs to be taken into account when controlling the shape or morphology of metal nanocrystals.

Twins in Cd1−xZnxS solid solution: Highly efficient photocatalyst for hydrogen generation from water

Cd1−xZnxS solid solution with nano-twin structures are synthesized and exhibit superior photocatalytic activities for H2 evolution from water under visible light irradiation (λ ≥ 430 nm) without noble metal co-catalysts. Such Cd0.5Zn0.5S nanocrystals show the highest activity for hydrogen evolution with an extremely high apparent quantum yield (AQY = 43%) at 425 nm, achieving a hydrogen evolution rate of 1.79 mmol h−1 without noble metals. The hydrogen evolution rate of 1.70 mmol h−1 was achieved under simulated sunlight conditions (without infrared light). The “back to back” potential formed by parallel nano-twins in the Cd1−xZnxS crystals can significantly improve the separation of the photo-generated electrons/holes (preventing their recombination) thus enhancing the photocatalytic activity. Photodeposition experiments of noble metals strongly support such a mechanism. It is found that noble metals were selectively photo-deposited at central regions between the twin boundaries. The concentration of free electrons at the central region of twins was markedly higher and the twins can effectively separate the H2 evolution sites (electrons) from oxidation reaction sites (holes).

Twin-induced one-dimensional homojunctions yield high quantum efficiency for solar hydrogen generation

Efficient charge separation is of crucial importance for the improvement of photocatalytic activity for solar hydrogen evolution. Here we report efficient photo-generated charge separation by twin-induced one-dimensional homojunctions with type-II staggered band alignment, using a ternary chalcogenate, i.e. Cd0.5Zn0.5S nanorod as a model material. The quantum efficiency of solar hydrogen evolution over this photocatalyst, without noble metal loading, reaches 62%. Unlike traditional heterojunctions, doping or combination of additional elements are not needed for the formation of this junction, which permits us to tune the band structures of semiconductors to the specific application in a more precise way. Our results highlight the power of forming long-range ordered homojunctions at the nanoscale for photocatalytic and photoelectrochemical applications.

Transformation of Pd Nanocubes into Octahedra with Controlled Sizes by Maneuvering the Rates of Etching and Regrowth

Palladium octahedra with controlled edge lengths were obtained from Pd cubes of a single size. The success of this synthesis relies on a transformation involving oxidative etching and regrowth. Because the {100} side faces of the Pd nanocubes were capped by Br(-) ions, Pd atoms were removed from the corners during oxidative etching, and the resultant Pd(2+) ions could be reduced and deposited back onto the nanocubes, but preferentially on the {100} facets. We could control the ratio of the etching and regrowth rates (R(etching) and R(regrowth)) simply by varying the amount of HCl added to the reaction solution. With a large amount of HCl, etching dominated the process (R(etching) ≫ R(regrowth)), resulting in the formation of Pd octahedra with an edge length equal to 70% of that of the cubes. In contrast, with a small amount of HCl, all of the newly formed Pd(2+) ions could be quickly reduced and deposited back onto the Pd cubes. In this case, R(etching) ≈ R(regrowth), and the resultant Pd octahedra had roughly the same volume as the starting cubes, together with an edge length equal to 130% of that of the cubes. When the amount of HCl was between these two extremes, we obtained Pd octahedra with intermediate edge lengths. This work not only advances our understanding of oxidative etching in nanocrystal synthesis but also offers a powerful means for controlling the shape and size of metal nanocrystals simply by adjusting the rates of etching and regrowth.

Facile synthesis of Pd–Ir bimetallic octapods and nanocages through galvanic replacement and co-reduction, and their use for hydrazine decomposition

This article describes a facile synthesis of Pd-Ir bimetallic nanostructures in the forms of core-shell octapods and alloyed nanocages. The success of this synthesis relies on the use of Pd nanocubes as the sacrificial templates and interplay of two different processes: the galvanic replacement between an Ir precursor and the Pd nanocubes and the co-reduction of Pd(2+) and Ir(3+) by ethylene glycol. The galvanic replacement played a dominant role in the initial stage, through which Pd atoms were dissolved from the side faces whereas Ir atoms were deposited at the corner sites to generate Pd-Ir core-shell octapods. As the concentration of Pd(2+) in the reaction mixture was increased, co-reduction of Pd(2+) and Ir(3+) occurred in the late stage of synthesis. The resultant Pd and Ir atoms were deposited onto the octapods while the Pd atoms in the interiors continued to be etched away due to the galvanic replacement, finally leading to the formation of Pd-Ir alloyed nanocages. The octapods and nanocages were then evaluated as catalysts for the selective generation of hydrogen from the decomposition of hydrous hydrazine. The nanocages exhibited better selectivity for hydrogen generation than octapods (66% versus 29%), which can be attributed to the presence of an alloyed, porous structure on the surface.

Synthesis of Mo-doped WO3 nanosheets with enhanced visible-light-driven photocatalytic properties

Ion doping provides a powerful means for the fabrication of a functionalized photocatalyst that is both active and stable. Herein, a series of Mo-doped monoclinic WO3 photocatalysts, in the form of well-shaped 2-dimension (2D) rectangular nanosheets, was successfully synthesized via a simple hydrothermal process. It is assumed that Mo was homogeneously doped into the crystal lattice of WO3. In addition to the 2D structure beneficial for charge transfer, Mo doping altered the band structure of WO3, enabling further improvement of the photocatalytic activity on rhodamine B degradation over the nanosheets.

Photocatalytic hydrogen production over CdS: effects of reaction atmosphere studied by in situ Raman spectroscopy

CdS is a well-known and efficient photocatalyst for photocatalytic hydrogen production. However, CdS is prone to photocorrosion in the photocatalytic reaction, in which CdS itself is oxidized by the photogenerated holes. Most of the work reported, to date, has focused only on the structure of CdS. However, less attention was paid to the kinetic changes of CdS during the photocatalytic reaction, which, in our opinion, is a crucial step for its practical utilization. In this report, we have developed a facile in situ Raman analysis, aiming to clarify the microstructural changes of CdS during the photocatalytic reaction process. In this study, photocatalytic hydrogen production over CdS in an Ar or air atmosphere was studied using various techniques in addition to in situ Raman spectroscopy. With Raman spectroscopy, a significant increase in the surface lattice strain of CdS was only observed when it was exposed to air, while the electron–phonon interactions remained the same regardless of the atmosphere. A direct correlation between the interfacial crystal lattice and photocorrosion of the CdS photocatalyst during photocatalytic hydrogen production was found based on our in situ Raman investigation. Finding the photocorrosion of the CdS photocatalyst at its very early stage using our in situ Raman technique is expected to provide meaningful guidance for the design of active and stable chalcogenide photocatalysts, which, however, cannot be achieved using traditional characterization techniques.

Towards efficient solar-to-hydrogen conversion: Fundamentals and recent progress in copper-based chalcogenide photocathodes

Abstract Photoelectrochemical (PEC) water splitting for hydrogen generation has been considered as a promising route to convert and store solar energy into chemical fuels. In terms of its large-scale application, seeking semiconductor photoelectrodes with high efficiency and good stability should be essential. Although an enormous number of materials have been explored for solar water splitting in the last several decades, challenges still remain for the practical application. P-type copper-based chalcogenides, such as Cu(In, Ga)Se2 and Cu2ZnSnS4, have shown impressive performance in photovoltaics due to narrow bandgaps, high absorption coefficients, and good carrier transport properties. The obtained high efficiencies in photovoltaics have promoted the utilization of these materials into the field of PEC water splitting. A comprehensive review on copper-based chalcogenides for solar-to-hydrogen conversion would help advance the research in this expanding area. This review will cover the physicochemical properties of copper-based chalco-genides, developments of various photocathodes, strategies to enhance the PEC activity and stability, introductions of tandem PEC cells, and finally, prospects on their potential for the practical solar-to-hydrogen conversion. We believe this review article can provide some insights of fundamentals and applications of copper-based chalco-genide thin films for PEC water splitting.

Surface Activation of Faceted Photocatalyst: When Metal Cocatalyst Determines the Nature of the Facets

Pt nanoparticles with tunable size are prepared on the entire surface of facet‐engineered Cu2WS4 decahedral photocatalyst via a kinetic‐controlled chemical reduction process. The {101} facets of the photocatalyst which featured photo‐oxidation, are successfully activated for photoreduction by Pt. The resulting photocatalyst shows an activity nine times higher compared to that of the only {001}‐facets activated catalyst obtained by a conventional in situ photodeposition route.

Functionalized nanostructures for enhanced photocatalytic performance under solar light.

Summary Photocatalytic hydrogen production from water has been considered to be one of the most promising solar-to-hydrogen conversion technologies. In the last decade, various functionalized nanostructures were designed to address the primary requirements for an efficient photocatalytic generation of hydrogen by using solar energy: visible-light activity, chemical stability, appropriate band-edge characteristics, and potential for low-cost fabrication. Our aim is to present a short review of our recent attempts that center on the above requirements. We begin with a brief introduction of photocatalysts coupling two or more semiconductors, followed by a further discussion of the heterostructures with improved matching of both band structures and crystal lattices. We then elaborate on the heterostructure design of the targeted materials from macroscopic regulation of compositions and phases, to the more precise control at the nanoscale, i.e., materials with the same compositions but different phases with certain band alignment. We conclude this review with perspectives on nanostructure design that might direct future research of this technology.