Generation of long-lived charges in organic semiconductor heterojunction nanoparticles for efficient photocatalytic hydrogen evolution

Koščo, Ján; González‐Carrero, Soranyel; Howells, Calvyn Travis; Teng, Fei; Dong, Yifan; Sougrat, Rachid; Harrison, George T.; Firdaus, Yuliar; Sheelamanthula, Rajendar; Purushothaman, Balaji; Moruzzi, Floriana; Xu, Weidong; Zhao, Lingyun; Basu, Aniruddha; Wolf, Stefaan De; Anthopoulos, Thomas D.; Durrant, James R.; McCulloch, Iain

doi:10.1038/s41560-022-00990-2

Cited by 217 publications

(277 citation statements)

References 53 publications

Supporting

Mentioning

228

Contrasting

Order By: Relevance

“…The PM6 features around 615 nm and 570 nm have similar peak intensities in the NPs and films. Interestingly, the absorption spectrum of the blend NPs exhibits some differences compared to the recently reported spectrum of 1:1 PM6:Y6 NPs (also prepared by the miniemulsion method); 16 the two spectra have differences in the relative intensity of the two PM6 peaks and the profile of the Y6 absorption. Again, this may be due to slight differences in preparation methods.…”

Section: Steady-state Absorption and Emissioncontrasting

confidence: 56%

“…NPs is weak, and is known to extend into the near-infrared, peaking at ∼930 nm. 16 Typically, fluorescence quenching of a donor when it is blended with a compatible acceptor indicates the formation of non-emissive species such as free charges. Similarly, fluorescence quenching of an electron acceptor can also occur when it is blended with a suitable donor.…”

Section: Steady-state Absorption and Emissionmentioning

confidence: 99%

“…11,13 NFAs have a number of advantages over the previous generation of (fullerene-based) acceptors, in particular much stronger visible light absorption. 11 A donor:NFA system that has demonstrated high performance, reaching PCEs greater than 17% in OPV cells [13][14][15] and having high photocatalytic H 2 production rates, 16 consists of donor-acceptor co-polymer PM6, and NFA Y6 (Figure 1a). In PM6:Y6 blend films, results from ultrafast spectroscopy have shown that free charges can be generated following excitation of either PM6 or Y6.…”

Section: Introductionmentioning

confidence: 99%

“…All organic donor:acceptor blends demonstrated so far have been HEPs using ascorbic acid as a sacrificial reagent for the oxidation pathway. 9,16 It has also been found that the use of noble metal co-catalysts increases the rate of H 2 production. 10 These co-catalysts are photo-deposited on the surface of the photocatalytic NP (Figure 1d), and provide well-defined sites for the reduction and/or oxidation half-reactions to take place.…”

Section: Introductionmentioning

confidence: 99%

“…They showed that the optimal PM6:Y6 mass ratio at 10% Pt loading is 7:3 PM6:Y6, and concluded that the high efficiency of this blend is due to the formation of remarkably long-lived free charges. 16 Interestingly, they also concluded that inefficient hole transfer from Y6 to PM6 is a limitation of the system, yet found that H 2 production by the 7:3 PM6:Y6 blend NPs is most efficient at 800 nm, where only Y6 absorbs light and subsequently undergoes hole transfer. Here, we show with ultrafast transient absorption (TA) spectroscopy that both electron and hole transfer are possible in 1:1 PM6:Y6 blend NPs.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Red-Light-Mediated Photocatalytic Hydrogen Evolution by Hole Transfer from Non-Fullerene Acceptor Y6

Kee

Perrelle

Dolan

et al. 2022

Preprint

View full text Add to dashboard Cite

One of the highest performing materials in organic photovoltaics is a blend of the polymer donor PM6 and non-fullerene acceptor (NFA) Y6. We report the use of 1:1 PM6:Y6 blend nanoparticles (NPs) prepared by the miniemulsion method for the photocatalytic production of hydrogen under sacrificial conditions, with a 2% mass loading of Pt co-catalyst. When pre- pared using TEBS, a thiophene-containing surfactant, these blend NPs have a desirable inter- mixed morphology. Under ≈1-sun illumination from 400 to 900 nm, hydrogen is produced at a rate of 8000 ± 400 μmol h−1 g−1, which is among the highest reported for organic photocata- lysts under similar conditions. Remarkably, this rate remains high at 5200 ± 300 μmol h−1 g−1 under 650 −900 nm excitation, where Y6 is exclusively excited, generating free charges by hole transfer from Y6 to PM6. The rate drops to 2400 ± 200 μmol h−1 g−1 at 400 −600 nm excitation, where PM6 is preferentially excited and free charges are generated from the conventional electron transfer mechanism. Additionally, external quantum efficiencies of 0.27 ± 0.08% at 405nm, 0.19 ± 0.04% at 565nm, and 0.22 ± 0.02% at 780nm were measured, indicating that this photocatalyst uses a broad region of solar spectrum to yield hydrogen from excitation of both the donor and the acceptor. Transient absorption spectroscopy results show that both hole transfer and electron transfer occur following the excitation of Y6 and PM6, respectively. This work is the first study to show that free charge generation via hole transfer is the dominant mechanism of hydrogen evolution in a donor:NFA blend. This work also highlights the potential that other donor:NFA blends may have for highly efficient green hydrogen production.

show abstract

Section: Steady-state Absorption and Emissioncontrasting

confidence: 56%

Section: Steady-state Absorption and Emissionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Red-Light-Mediated Photocatalytic Hydrogen Evolution by Hole Transfer from Non-Fullerene Acceptor Y6

Kee

Perrelle

Dolan

et al. 2022

Preprint

View full text Add to dashboard Cite

show abstract

Enhanced Photocatalytic Hydrogen Evolution from Organic Ternary Heterojunction Nanoparticles Featuring a Compact Alloy‐Like Phase

Yang

Cai

et al. 2022

Adv Funct Materials

View full text Add to dashboard Cite

Organic semiconductor nanoparticles (NPs) are attractive photocatalysts to produce hydrogen from water splitting. Herein, a ternary strategy of incorporating crystalline n-type molecule IDMIC-4F into the host system made of p-type polymer PM6 and n-type molecule ITCC-M is demonstrated. ITCC-M and IDMIC-4F form compact alloy-like composite with shorter lattice spacing in the ternary p/n heterojunction NPs, resulting in enhanced exciton dissociation and charge transfer characteristics. As the result, an unprecedented hydrogen evolution rate (HER) of 307 mmol h −1 g −1 and a maximum apparent quantum efficiency of 5.9% at 600 nm are achieved in the optimized ternary NPs (PM6:ITCC-M:IDMIC-4F = 1:1.3:0.2), which is among the highest HER from organic photocatalysts to the best of the authors' knowledge. The alloylike composite also improves the operational stability of ternary NP photocatalysts. This study shows that synergizing two compatible n-type small molecules to form alloy-like composite is a promising approach to design novel organic photocatalysts for boosting the photocatalytic hydrogen evolution efficiency.

show abstract

Mo‐Modified ZnIn₂S₄@NiTiO₃ S‐Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible‐Light‐Driven Hydrogen Evolution

Zhu

Tao

et al. 2023

Adv Funct Materials

View full text Add to dashboard Cite

Designing and developing visible-light-responsive materials for solar to chemical energy is an efficient and promising approach to green and sustainable carbon-neutral energy systems. Herein, a facile in situ growth hydrothermal strategy using Mo-modified ZnIn 2 S 4 (Mo-ZIS) nanosheets coupled with NiTiO 3 (NTO) microrods to synthesize multifunctional Mo-modified ZIS wrapped NTO microrods (Mo-ZIS@NTO) photocatalyst with enhanced interfacial electric field (IEF) effect and typical S-scheme heterojunction is reported. Mo-ZIS@NTO catalyst possesses wide-spectrum light absorption properties, excellent visible light-to-thermal energy effect, electron mobility, charges transfer, and strong IEF and exhibits excellent solar-to-chemical energy conversion for efficient visible-light-driven photocatalytic hydrogen evolution. Notably, the engineered Mo 1.4 -ZIS@NTO catalyst exhibits superior performance with H 2 evolution rate of up to 14.06 mmol g −1 h − 1 and the apparent quantum efficiency of 44.1% at 420 nm. The scientific explorations provide an in-depth understanding of microstructure, S-scheme heterojunction, enhanced IEF, Mo-dopant facilitation effect. Moreover, the theoretical simulations verify the critical role of Mo element in promoting the adsorption and activation of H 2 O molecules, modulating the H adsorption behavior on active S sites, and thus accelerating the overall catalytic efficiency. The photocatalytic hydrogen evolution mechanism via S-scheme heterojunction with adjustable IEF regulation over Mo 1.4 -ZIS@NTO is also demonstrated.

show abstract

Generation of long-lived charges in organic semiconductor heterojunction nanoparticles for efficient photocatalytic hydrogen evolution

Cited by 217 publications

References 53 publications

Red-Light-Mediated Photocatalytic Hydrogen Evolution by Hole Transfer from Non-Fullerene Acceptor Y6

Red-Light-Mediated Photocatalytic Hydrogen Evolution by Hole Transfer from Non-Fullerene Acceptor Y6

Enhanced Photocatalytic Hydrogen Evolution from Organic Ternary Heterojunction Nanoparticles Featuring a Compact Alloy‐Like Phase

Mo‐Modified ZnIn₂S₄@NiTiO₃ S‐Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible‐Light‐Driven Hydrogen Evolution

Contact Info

Product

Resources

About

Generation of long-lived charges in organic semiconductor heterojunction nanoparticles for efficient photocatalytic hydrogen evolution

Cited by 217 publications

References 53 publications

Red-Light-Mediated Photocatalytic Hydrogen Evolution by Hole Transfer from Non-Fullerene Acceptor Y6

Red-Light-Mediated Photocatalytic Hydrogen Evolution by Hole Transfer from Non-Fullerene Acceptor Y6

Enhanced Photocatalytic Hydrogen Evolution from Organic Ternary Heterojunction Nanoparticles Featuring a Compact Alloy‐Like Phase

Mo‐Modified ZnIn2S4@NiTiO3 S‐Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible‐Light‐Driven Hydrogen Evolution

Contact Info

Product

Resources

About

Mo‐Modified ZnIn₂S₄@NiTiO₃ S‐Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible‐Light‐Driven Hydrogen Evolution