Photocatalytically Active Superstructures of Quantum Dots and Iron Porphyrins for Reduction of CO2 to CO in Water

Lian, Shichen; Kodaimati, Mohamad S.; Weiss, Emily A.

doi:10.1021/acsnano.7b07377

Title: Photocatalytically Active Superstructures of Quantum Dots and Iron Porphyrins for Reduction of CO₂ to CO in Water

Journal Article · Wed Jan 03 00:00:00 EST 2018 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.7b07377· OSTI ID:1470146

Lian, Shichen ^[1]; Kodaimati, Mohamad S. ^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)

In this paper, we describe the use of electrostatic assemblies of negatively charged colloidal CuInS₂/ZnS quantum dot (QD) sensitizers and positively charged, trimethylamino-functionalized iron tetraphenylporphyrin catalysts (FeTMA) to photoreduce CO₂ to CO in water upon illumination with 450 nm light. This system achieves a turnover number (TON) of CO (per FeTMA) of 450 after 30 h of illumination, with a selectivity of 99%. Its sensitization efficiency (TON per Joule of photons absorbed) is a factor of 11 larger than the previous record for photosensitization of an iron porphyrin catalyst for this reaction, held by a system in which both QDs and metal porphyrin were uncharged. Steady-state and time-resolved optical spectroscopy provides evidence for electrostatic assembly of QDs and FeTMA. Control of the size of the assemblies with addition of a screening counterion, K⁺, and a correlation between their measured size and their catalytic activity, indicates that the enhancement in performance of this system over the analogous uncharged system is due to the proximity of the FeTMA catalyst to multiple light-absorbing QDs and the selective formation of QD–FeTMA contacts (rather than QD–QD or FeTMA–FeTMA contacts). Finally, this system therefore shows the ability to funnel photoinduced electrons to a reaction center, which is crucial for carrying out reactions that require multistep redox processes under low photon flux, and thus is an important advance in developing artificial photocatalytic systems that function in natural light.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0000989; AC02-06CH11357

OSTI ID:: 1470146

Journal Information:: ACS Nano, Vol. 12, Issue 1; Related Information: CBES partners with Northwestern University (lead); Harvard University; New York University; Pennsylvania State University; University of Michigan; University of Pittsburgh; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 109 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrostatic self-assembly
copper indium sulfide
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artificial photosynthesis
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Title: Photocatalytically Active Superstructures of Quantum Dots and Iron Porphyrins for Reduction of CO2 to CO in Water

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Title: Photocatalytically Active Superstructures of Quantum Dots and Iron Porphyrins for Reduction of CO₂ to CO in Water