Near-infrared photon upconversion and solar synthesis using lead-free nanocrystals

Nie, Chengming; Du, Jun; Han, Yaoyao; Zhao, Guoqing; Yang, Fan; Liang, Guijie; Wu, Kaifeng

doi:10.1038/s41566-023-01156-6

Cited by 68 publications

(48 citation statements)

References 57 publications

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“…Many different types of biphotonic processes have been uncovered, ,− among which sensitized triplet–triplet annihilation upconversion (sTTA-UC) is particularly promising. While upconversion has been intensively investigated from a photophysical perspective for applications in lighting and solar energy harvesting, − its use in photoredox catalysis is a relatively recent development. − Several non-catalytic photochemical reactions driven by upconversion have furthermore drawn interest. − …”

Section: Introductionmentioning

confidence: 99%

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Wang

Glaser

et al. 2023

J. Am. Chem. Soc.

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Sensitized triplet−triplet annihilation upconversion is a promising strategy to use visible light for chemical reactions requiring the energy input of UV photons. This strategy avoids unsafe ultraviolet light sources and can mitigate photo-damage and provide access to reactions, for which filter effects hamper direct UV excitation. Here, we report a new approach to make blue-to-UV upconversion more amenable to photochemical applications. The tethering of a naphthalene unit to a cyclometalated iridium(III) complex yields a bichromophore with a high triplet energy (2.68 eV) and a naphthalenebased triplet reservoir featuring a lifetime of 72.1 μs, roughly a factor of 20 longer than the photoactive excited state of the parent iridium(III) complex. In combination with three different annihilators, consistently lower thresholds for the blue-to-UV upconversion to crossover from a quadratic into a linear excitation power dependence regime were observed with the bichromophore compared to the parent iridium(III) complex. The upconversion system composed of the bichromophore and the 2,5-diphenyloxazole annihilator is sufficiently robust under long-term blue irradiation to continuously provide a high-energy singlet-excited state that can drive chemical reactions normally requiring UV light. Both photoredox and energy transfer catalyses were feasible using this concept, including the reductive N−O bond cleavage of Weinreb amides, a C−C coupling reaction based on reductive aryl debromination, and two Paterno−Buchi [2 + 2] cycloaddition reactions. Our work seems relevant in the context of developing new strategies for driving energetically demanding photochemistry with low-energy input light.

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Section: Introductionmentioning

confidence: 99%

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Wang

Glaser

et al. 2023

J. Am. Chem. Soc.

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“…A vast library of ligand exchange protocols has been developed and tailored for a multitude of applications. For example, NC-based photovoltaics benefit from the introduction of ligands with short alkyl chains or halide ligands on the NC surface, because these ligands optimize the NC packing density and favor efficient charge transport. , Further, synergistic enhancement of heterogeneous catalysts has been attained by grafting organic species or organometallic complexes to the NC surface. − Finally, NCs functionalized with polyaromatic hydrocarbon (PAH) ligands have emerged as excellent triplet exciton based sensitizers with applications in photocatalysis, ,− optoelelctronics, , optogenetics, , and bioimaging. − …”

Section: Introductionmentioning

confidence: 99%

Colloidal-ALD-Grown Metal Oxide Shells Enable the Synthesis of Photoactive Ligand/Nanocrystal Composite Materials

et al. 2023

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Colloidal nanocrystals (NCs) are ideal materials for a variety of applications and devices, which span from catalysis and optoelectronics to biological imaging. Organic chromophores are often combined with NCs as photoactive ligands to expand the functionality of NCs or to achieve optimal device performance. The most common methodology to introduce these chromophores involves ligand exchange procedures. Despite their ubiquitous nature, ligand exchanges suffer from a few limitations, which include reversible binding, restricted access to binding sites, and the need for purification of the samples, which can result in loss of colloidal stability. Herein, we propose a methodology to bypass these inherent issues of ligand exchange through the growth of an amorphous alumina shell by colloidal atomic layer deposition (c-ALD). We demonstrate that c-ALD creates colloidally stable composite materials, which comprise NCs and organic chromophores as photoactive ligands, by trapping the chromophores around the NC core. As representative examples, we functionalize semiconductor NCs, which include PbS, CsPbBr 3 , CuInS 2 , Cu 2−x X, and lanthanide-based upconverting NCs, with polyaromatic hydrocarbons (PAH) ligands. Finally, we prove that triplet energy transfer occurs through the shell and we realize the assembly of a triplet exciton funnel structure, which cannot be obtained via conventional ligand exchange procedures. The formation of these organic/inorganic hybrid shells promises to synergistically boost catalytic and multiexcitonic processes while endowing enhanced stability to the NC core.

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“…Halide double perovskites like Cs 2 NaInCl 6 are environmentally benign with a wide band gap of ∼5.1 eV (243 nm). , Because of the wide band gap, Cs 2 NaInCl 6 does not interact with most parts of ultraviolet–visible (UV–vis) radiation, making them photostable. Importantly, ions like In 3+ have an octahedral coordination, and therefore, big lanthanide ions can be doped in Cs 2 NaInCl 6 . − Lanthanide ions like Er 3+ and Yb 3+ can emit short-wave infrared (SWIR) radiations, which are important for optical fiber communication, security cameras, food processing and storing, bioimaging, and so on. − These SWIR radiations are due to f–f electronic transitions of the lanthanide ions, but the optical excitation of the same f-electrons is Laporte forbidden . One solution to this problem is to codope lanthanides with another dopant that can absorb light.…”

Section: Introductionmentioning

confidence: 99%

Short-Wave Infrared Emissions from Te⁴⁺–Ln³⁺ (Ln: Er, Yb)-Codoped Cs₂NaInCl₆ Double Perovskites

Arfin,

Rathod,

Shingote

et al. 2023

Chem. Mater.

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A Cs 2 NaInCl 6 double perovskite is environmentally benign, and its wide band gap (∼5.1 eV) makes it photoinactive and photostable in the ultraviolet, visible, and short-wave infrared (SWIR) regions. Interestingly, the octahedrally coordinated In 3+ lattice site is suitable for doping lanthanide ions like Er 3+ and Yb 3+ , which can emit SWIR radiation at 1540 nm (0.805 eV) and 994 nm (1.247 eV), respectively. But the optical excitation of lanthanides is Laporte forbidden, and the host requires excitation energy >5.1 eV. The large Stokes shift for the excitation and SWIR emission reduces the power conversion efficiency. Here, we codoped Te 4+ with Er 3+ or Yb 3+ into Cs 2 NaInCl 6 . Te 4+ absorbs at the sub-band-gap level at around 3.1 eV (400 nm) because of 5s 2 → 5s 1 5p 1 electronic transitions. Then, the excited Te 4+ transfers its energy nonradiatively to an Er 3+ or Yb 3+ codopant. The de-excitation of Er 3+ or Yb 3+ through f−f electronic transitions emits SWIR radiation at 1540 and 994 nm, respectively, along with weak visible-light emissions. Temperature (8−300 K) dependent photoluminescence excitation, emission, and lifetime measurements reveal the mechanism of these energy transfer processes. Finally, we fabricated a simple phosphorconverted light-emitting diode (pc-LED) emitting SWIR radiation.

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Near-infrared photon upconversion and solar synthesis using lead-free nanocrystals

Cited by 68 publications

References 57 publications

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Colloidal-ALD-Grown Metal Oxide Shells Enable the Synthesis of Photoactive Ligand/Nanocrystal Composite Materials

Short-Wave Infrared Emissions from Te⁴⁺–Ln³⁺ (Ln: Er, Yb)-Codoped Cs₂NaInCl₆ Double Perovskites

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Near-infrared photon upconversion and solar synthesis using lead-free nanocrystals

Cited by 68 publications

References 57 publications

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Colloidal-ALD-Grown Metal Oxide Shells Enable the Synthesis of Photoactive Ligand/Nanocrystal Composite Materials

Short-Wave Infrared Emissions from Te4+–Ln3+ (Ln: Er, Yb)-Codoped Cs2NaInCl6 Double Perovskites

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Short-Wave Infrared Emissions from Te⁴⁺–Ln³⁺ (Ln: Er, Yb)-Codoped Cs₂NaInCl₆ Double Perovskites