As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Lanthanide-doped upconversion nanoparticles (UCNPs) are capable of converting near-infra-red excitation into visible and ultraviolet emission. Their unique optical properties have advanced a broad range of applications, such as fluorescent microscopy, deep-tissue bioimaging, nanomedicine, optogenetics, security labelling and volumetric display. However, the constraint of concentration quenching on upconversion luminescence has hampered the nanoscience community to develop bright UCNPs with a large number of dopants. This review surveys recent advances in developing highly doped UCNPs, highlights the strategies that bypass the concentration quenching effect, and discusses new optical properties as well as emerging applications enabled by these nanoparticles.

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Advances in highly doped upconversion nanoparticles

Defect engineering in photocatalytic materials

Excitonic effects mediated by Coulomb interactions between photogenerated electrons and holes play crucial roles in photoinduced processes of semiconductors. In terms of photocatalysis, however, efforts have seldom been devoted to the relevant aspects. For the catalysts with giant excitonic effects, the coexisting, competitive exciton generation serves as a key obstacle to the yield of free charge carriers, and hence, transformation of excitons into free carriers would be beneficial for optimizing the charge-carrier-involved photocatalytic processes. Herein, by taking bismuth oxybromide (BiOBr) as a prototypical model system, we demonstrate that excitons can be effectively dissociated into charge carriers with the incorporation of oxygen vacancy, leading to excellent performances in charge-carrier-involved photocatalytic reactions such as superoxide generation and selective organic syntheses under visible-light illumination. This work not only establishes an in-depth understanding of defective structures ...

Oxygen-Vacancy-Mediated Exciton Dissociation in BiOBr for Boosting Charge-Carrier-Involved Molecular Oxygen Activation

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

Forging Colloidal Nanostructures via Cation Exchange Reactions

Triplet excitons are pervasive in both organic and inorganic semiconductors but generally remain confined to the material in which they originate. We demonstrated by transient absorption spectroscopy that cadmium selenide semiconductor nanoparticles, selectively excited by green light, engage in interfacial Dexter-like triplet-triplet energy transfer with surface-anchored polyaromatic carboxylic acid acceptors, extending the excited-state lifetime by six orders of magnitude. Net triplet energy transfer also occurs from surface acceptors to freely diffusing molecular solutes, further extending the lifetime while sensitizing singlet oxygen in an aerated solution. The successful translation of triplet excitons from semiconductor nanoparticles to the bulk solution implies that such materials are generally effective surrogates for molecular triplets. The nanoparticles could thereby potentially sensitize a range of chemical transformations that are relevant for fields as diverse as optoelectronics, solar energy conversion, and photobiology.

http://science.sciencemag.org/content/sci/351/6271/369.full.pdf

Direct observation of triplet energy transfer from semiconductor nanocrystals.

The ability of metal nanoparticles to capture light through plasmon excitations offers an opportunity for enhancing the optical absorption of plasmon-coupled semiconductor materials via energy transfer. This process, however, requires that the semiconductor component is electrically insulated to prevent a "backward" charge flow into metal and interfacial states, which causes a premature dissociation of excitons. Here we demonstrate that such an energy exchange can be achieved on the nanoscale by using nonepitaxial Au/CdS core/shell nanocomposites. These materials are fabricated via a multistep cation exchange reaction, which decouples metal and semiconductor phases leading to fewer interfacial defects. Ultrafast transient absorption measurements confirm that the lifetime of excitons in the CdS shell (τ ≈ 300 ps) is much longer than lifetimes of excitons in conventional, reduction-grown Au/CdS heteronanostructures. As a result, the energy of metal nanoparticles can be efficiently utilized by the semiconductor component without undergoing significant nonradiative energy losses, an important property for catalytic or photovoltaic applications. The reduced rate of exciton dissociation in the CdS domain of Au/CdS nanocomposites was attributed to the nonepitaxial nature of Au/CdS interfaces associated with low defect density and a high potential barrier of the interstitial phase.

/pdf/enhanced-lifetime-of-excitons-in-nonepitaxial-au-cds-core-3qs9omm331.pdf

Enhanced Lifetime of Excitons in Nonepitaxial Au/CdS Core/Shell Nanocrystals

Colloidal nanocrystal solids represent an emerging class of functional materials that hold strong promise for device applications. The macroscopic properties of these disordered assemblies are determined by complex trajectories of exciton diffusion processes, which are still poorly understood. Owing to the lack of theoretical insight, experimental strategies for probing the exciton dynamics in quantum dot solids are in great demand. Here, we develop an experimental technique for mapping the motion of excitons in semiconductor nanocrystal films with a subdiffraction spatial sensitivity and a picosecond temporal resolution. This was accomplished by doping PbS nanocrystal solids with metal nanoparticles that force the exciton dissociation at known distances from their birth. The optical signature of the exciton motion was then inferred from the changes in the emission lifetime, which was mapped to the location of exciton quenching sites. By correlating the metal–metal interparticle distance in the film with ...

Mapping the exciton diffusion in semiconductor nanocrystal solids.

Recent progress in the colloidal synthesis of inorganic nanocrystals has led to the realization of complex, multidomain nanoparticle morphologies that give rise to advanced optoelectronic properties. Such nanocomposites are particularly appealing for photocatalytic applications where tunable absorption, extensive charge separation, and large surface-to-volume ratios are important. To date, heterostructured nanocrystals featuring a metal catalyst and a semiconductor “chromophore” component have shown compelling efficiencies in photoreduction reactions, including sacrificial hydrogen production. Time-resolved optical studies have attributed their success to a near-complete separation of photoinduced charges across dissimilar nanoparticle domains. The spectroscopy approach has also identified the key performance-limiting factors of nanocrystal catalysts that arise from inefficient extraction of photoinduced charges to catalytic sites. Along these lines, the main scope of present-day efforts targets the impro...

Photocatalytic Applications of Colloidal Heterostructured Nanocrystals: What's Next?

The emerging generation of quantum dot optoelectronic devices offers an appealing prospect of a size-tunable band gap The confinement-enabled control over electronic properties, however, requires nanoparticles to be sufficiently small, which leads to a large area of interparticle boundaries in a film Such interfaces lead to a high density of surface traps which ultimately increase the electrical resistance of a solid To address this issue, we have developed an inverse energy-gradient core/shell architecture supporting the quantum confinement in nanoparticles larger than the exciton Bohr radius The assembly of such nanostructures exhibits a relatively low surface-to-volume ratio, which was manifested in this work through the enhanced conductance of solution-processed films The reported core/shell geometry was realized by growing a narrow gap semiconductor layer (CdSe) on the surface of a wide-gap core material (CdS) promoting the localization of excitons in the shell domain, as was confirmed by ultraf

http://pubs.acs.org/doi/pdf/10.1021/jacs.7b02054

Natalia Razgoniaeva

Papers

Direct observation of triplet energy transfer from semiconductor nanocrystals.

Enhanced Lifetime of Excitons in Nonepitaxial Au/CdS Core/Shell Nanocrystals

Mapping the exciton diffusion in semiconductor nanocrystal solids.

Photocatalytic Applications of Colloidal Heterostructured Nanocrystals: What's Next?

One-Dimensional Carrier Confinement in “Giant” CdS/CdSe Excitonic Nanoshells