Colloidal nano-MOFs nucleate and stabilize ultra-small quantum dots of lead bromide perovskites

Loredana Protesescu; Joaquín Calbo; Kristopher Williams; William Tisdale; Aron Walsh; Mircea Dincǎ

doi:10.1039/d1sc00282a

Colloidal nano-MOFs nucleate and stabilize ultra-small quantum dots of lead bromide perovskites

Loredana Protesescu, Joaquín Calbo, Kristopher Williams, William Tisdale, Aron Walsh, Mircea Dincǎ

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host-guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr3O(OH)(H2O)2(terephthalate)3 (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr3, MAPbBr3 (MA+ = methylammonium), and (FA)PbBr3 (FA+ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr3 (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.

Original language	English
Pages (from-to)	6129-6135
Number of pages	7
Journal	Chemical Science
Volume	12
Issue number	17
DOIs	https://doi.org/10.1039/d1sc00282a
Publication status	Published - 2021 May 7

Bibliographical note

Funding Information:
This work was supported by the Army Research Office (grant number W911NF-17-1-0174). We thank Dr R. Day for SEM and Dr J. Gardener for assistance with STEM EDX mapping. L. P. acknowledges the Swiss NSF Postdoctoral Fellowship for support (Grant P2EXP2-172214). J. C. acknowledges the Gen-eralitat Valenciana for the Postdoctoral APOSTD/2017/081 Fellowship. K. W. and W. A. T. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0019345. This research was also supported by the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (2018M3D1A1058536). Computational work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) via the HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). We thank Mr G. Skorupskii for generating graphics for Fig. 1.

Publisher Copyright:
© The Royal Society of Chemistry.

All Science Journal Classification (ASJC) codes

Chemistry(all)

Access to Document

10.1039/d1sc00282a

Cite this

@article{0a1c49901e104ac795ccdc5dc8c28361,

title = "Colloidal nano-MOFs nucleate and stabilize ultra-small quantum dots of lead bromide perovskites",

abstract = "The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host-guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr3O(OH)(H2O)2(terephthalate)3 (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr3, MAPbBr3 (MA+ = methylammonium), and (FA)PbBr3 (FA+ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr3 (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.",

author = "Loredana Protesescu and Joaqu{\'i}n Calbo and Kristopher Williams and William Tisdale and Aron Walsh and Mircea Dincǎ",

note = "Funding Information: This work was supported by the Army Research Office (grant number W911NF-17-1-0174). We thank Dr R. Day for SEM and Dr J. Gardener for assistance with STEM EDX mapping. L. P. acknowledges the Swiss NSF Postdoctoral Fellowship for support (Grant P2EXP2-172214). J. C. acknowledges the Gen-eralitat Valenciana for the Postdoctoral APOSTD/2017/081 Fellowship. K. W. and W. A. T. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0019345. This research was also supported by the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (2018M3D1A1058536). Computational work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) via the HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). We thank Mr G. Skorupskii for generating graphics for Fig. 1. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2021",

month = may,

day = "7",

doi = "10.1039/d1sc00282a",

language = "English",

volume = "12",

pages = "6129--6135",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "17",

}

TY - JOUR

T1 - Colloidal nano-MOFs nucleate and stabilize ultra-small quantum dots of lead bromide perovskites

AU - Protesescu, Loredana

AU - Calbo, Joaquín

AU - Williams, Kristopher

AU - Tisdale, William

AU - Walsh, Aron

AU - Dincǎ, Mircea

N1 - Funding Information: This work was supported by the Army Research Office (grant number W911NF-17-1-0174). We thank Dr R. Day for SEM and Dr J. Gardener for assistance with STEM EDX mapping. L. P. acknowledges the Swiss NSF Postdoctoral Fellowship for support (Grant P2EXP2-172214). J. C. acknowledges the Gen-eralitat Valenciana for the Postdoctoral APOSTD/2017/081 Fellowship. K. W. and W. A. T. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0019345. This research was also supported by the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (2018M3D1A1058536). Computational work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) via the HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). We thank Mr G. Skorupskii for generating graphics for Fig. 1. Publisher Copyright: © The Royal Society of Chemistry.

PY - 2021/5/7

Y1 - 2021/5/7

N2 - The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host-guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr3O(OH)(H2O)2(terephthalate)3 (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr3, MAPbBr3 (MA+ = methylammonium), and (FA)PbBr3 (FA+ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr3 (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.

AB - The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host-guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr3O(OH)(H2O)2(terephthalate)3 (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr3, MAPbBr3 (MA+ = methylammonium), and (FA)PbBr3 (FA+ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr3 (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.

UR - http://www.scopus.com/inward/record.url?scp=85105576047&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85105576047&partnerID=8YFLogxK

U2 - 10.1039/d1sc00282a

DO - 10.1039/d1sc00282a

M3 - Article

AN - SCOPUS:85105576047

SN - 2041-6520

VL - 12

SP - 6129

EP - 6135

JO - Chemical Science

JF - Chemical Science

IS - 17

ER -

Colloidal nano-MOFs nucleate and stabilize ultra-small quantum dots of lead bromide perovskites

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this