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Frustrated Lewis pairs engineering via dopant-defect coupling in quantum dots for spatial regulation of proton and electron utilization in CO2 photoreduction to oxygenated products

Cao, Yuehan ; Zhou, Yu ; Zheng, Heng ; Wang, Dajun ; Liu, Yucheng ; Zhang, Tongxi ; Li, Lina ; Pullerits, Tõnu LU orcid ; Zhou, Ying and Zheng, Kaibo LU (2026) In Nano Energy 157.
Abstract

Solar-driven photocatalytic CO2 reduction to highly reduced, energy-dense oxygenated products is hindered by sluggish proton-coupled electron transfer and hydrogenation steps. Conventional strategies that separate redox centers reduce charge recombination but limit proton transfer from water oxidation. Here, we address this trade-off by constructing dopant-defect-coupled frustrated Lewis pairs (FLPs) in CdS quantum dots (QDs) by controlled Cu doping. Cu⁺ dopant and adjacent surface vacancies form Cu⁺–Vₛ pairs that generate strong interfacial electric dipoles, enabling polarized activation of O–H bonds in water and C–O bonds in adsorbed CO*. Time-resolved spectroscopic studies demonstrate these FLPs can spatially stabilize... (More)

Solar-driven photocatalytic CO2 reduction to highly reduced, energy-dense oxygenated products is hindered by sluggish proton-coupled electron transfer and hydrogenation steps. Conventional strategies that separate redox centers reduce charge recombination but limit proton transfer from water oxidation. Here, we address this trade-off by constructing dopant-defect-coupled frustrated Lewis pairs (FLPs) in CdS quantum dots (QDs) by controlled Cu doping. Cu⁺ dopant and adjacent surface vacancies form Cu⁺–Vₛ pairs that generate strong interfacial electric dipoles, enabling polarized activation of O–H bonds in water and C–O bonds in adsorbed CO*. Time-resolved spectroscopic studies demonstrate these FLPs can spatially stabilize photogenerated holes and electrons at the ground state Lewis basic site and the neighboring Lewis acid site, respectively, without rapid charge recombination. In-situ FTIR and theoretical calculations confirm that such FLPs enhance water oxidation through O–H bond polarized cleavage, creating a proton-rich environment while simultaneously promoting CO* hydrogenation at nearby reduction sites to form key intermediates (HCO* and H3CO*), leading to improved production of highly reduced oxygenated products. Consequently, the optimally doped QDs demonstrate robust stability over five consecutive cycles, alongside a 1.4-fold enhancement in the total yield of oxygenated products over pure CdS and 94% overall selectivity for highly reduced oxygenated products.

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author
; ; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Frustrated lewis pairs, Noble-metal-free catalysts, Photocatalytic COreduction, Quantum dots
in
Nano Energy
volume
157
article number
112232
publisher
Elsevier
external identifiers
  • scopus:105045337881
ISSN
2211-2855
DOI
10.1016/j.nanoen.2026.112232
language
English
LU publication?
yes
id
70900b69-3de8-4253-a158-059f28536a83
date added to LUP
2026-09-28 11:54:50
date last changed
2026-09-28 11:55:05
@article{70900b69-3de8-4253-a158-059f28536a83,
  abstract     = {{<p>Solar-driven photocatalytic CO<sub>2</sub> reduction to highly reduced, energy-dense oxygenated products is hindered by sluggish proton-coupled electron transfer and hydrogenation steps. Conventional strategies that separate redox centers reduce charge recombination but limit proton transfer from water oxidation. Here, we address this trade-off by constructing dopant-defect-coupled frustrated Lewis pairs (FLPs) in CdS quantum dots (QDs) by controlled Cu doping. Cu⁺ dopant and adjacent surface vacancies form Cu⁺–Vₛ pairs that generate strong interfacial electric dipoles, enabling polarized activation of O–H bonds in water and C–O bonds in adsorbed CO*. Time-resolved spectroscopic studies demonstrate these FLPs can spatially stabilize photogenerated holes and electrons at the ground state Lewis basic site and the neighboring Lewis acid site, respectively, without rapid charge recombination. In-situ FTIR and theoretical calculations confirm that such FLPs enhance water oxidation through O–H bond polarized cleavage, creating a proton-rich environment while simultaneously promoting CO* hydrogenation at nearby reduction sites to form key intermediates (HCO* and H<sub>3</sub>CO*), leading to improved production of highly reduced oxygenated products. Consequently, the optimally doped QDs demonstrate robust stability over five consecutive cycles, alongside a 1.4-fold enhancement in the total yield of oxygenated products over pure CdS and 94% overall selectivity for highly reduced oxygenated products.</p>}},
  author       = {{Cao, Yuehan and Zhou, Yu and Zheng, Heng and Wang, Dajun and Liu, Yucheng and Zhang, Tongxi and Li, Lina and Pullerits, Tõnu and Zhou, Ying and Zheng, Kaibo}},
  issn         = {{2211-2855}},
  keywords     = {{Frustrated lewis pairs; Noble-metal-free catalysts; Photocatalytic COreduction; Quantum dots}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Nano Energy}},
  title        = {{Frustrated Lewis pairs engineering via dopant-defect coupling in quantum dots for spatial regulation of proton and electron utilization in CO<sub>2</sub> photoreduction to oxygenated products}},
  url          = {{http://dx.doi.org/10.1016/j.nanoen.2026.112232}},
  doi          = {{10.1016/j.nanoen.2026.112232}},
  volume       = {{157}},
  year         = {{2026}},
}