skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: On the myth of “red/near-IR carbon quantum dots” from thermal processing of specific colorless organic precursors
Carbon dots were originally found and reported as surface-passivated small carbon nanoparticles, where the effective surface passivation was the chemical functionalization of the carbon nanoparticles with organic molecules. Understandably, the very broad optical absorptions of carbon dots are largely the same as those intrinsic to the carbon nanoparticles, characterized by progressively decreasing absorptivities from shorter to longer wavelengths. Thus, carbon dots are generally weak absorbers in the red/near-IR and correspondingly weak emitters with low quantum yields. Much effort has been made on enhancing the optical performance of carbon dots in the red/near-IR, but without meaningful success due to the fact that optical absorptivities defined by Mother Nature are in general rather inert to any induced alterations. Nevertheless, there were shockingly casual claims in the literature on the major success in dramatically altering the optical absorption profiles of “carbon dots” by simply manipulating the dot synthesis to produce samples of some prominent optical absorption bands in the red/near-IR. Such claims have found warm receptions in the research field with a desperate need for carbon dots of the same optical performance in the red/near-IR as that in the green and blue. However, by looking closely at the initially reported synthesis and all its copies in subsequent investigations on the “red/near-IR carbon dots”, one would find that the “success” of the synthesis by thermal or hydrothermal carbonization processing requires specific precursor mixtures of citric acid with formamide or urea. In the study reported here, the systematic investigation included precursor mixtures of citric acid with not only formamide or urea but also their partially methylated or permethylated derivatives for the carbonization processing under conditions similar to and beyond those commonly used and reported in the literature. Collectively all of the results are consistent only with the conclusion that the origins of the observed red/near-IR optical absorptions in samples from some of the precursor mixtures must be molecular chromophores from thermally induced chemical reactions, nothing to do with any nanoscale carbon entities produced by carbonization.  more » « less
Award ID(s):
1701399 1701424
PAR ID:
10284465
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Nanoscale Advances
Volume:
3
Issue:
14
ISSN:
2516-0230
Page Range / eLocation ID:
4186 to 4195
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; (, C)
    The commercially acquired aqueous solution of “carbon quantum dots” sample was evaluated by optical absorption and fluorescence emission methods; in reference to aqueous dispersed small carbon nanoparticles and representative carbon dots prepared from chemical functionalization of the carbon nanoparticles. The results suggest a very low content of carbon that is associated with nanoscale carbon particles/domains in the as-supplied sample; and likely significant contamination by dye-like species/mixtures. In the absence of any information on the synthesis and history of the commercial sample, the possible cause of the contamination was illustrated by an example on similar dye formation in the one-pot carbonization synthesis of “red carbon dots” from citric acid–formamide precursor mixtures under too mild processing conditions that were insufficient for the intended carbonization. The negative impacts to the carbon dots research field by the apparent proliferation and now commercial availability of carbon-deficient or even largely carbon-less “carbon quantum dots”, which are more susceptible to dye contamination or dominance, are discussed. 
    more » « less
  2. ; ; ; (, RSC Advances)
    Carbon dots (CDs) synthesis from citric acid, ethylenediamine, and formamide by microwave-assisted hydrothermal carbonization in a pressurized vessel. 
    more » « less
  3. ; ; ; ; ; ; (, C)
    Carbon dots (CDots) are generally defined as small carbon nanoparticles (CNPs) with effective surface passivation, for which the classical synthesis is the functionalization of pre-existing CNPs with organic molecules. However, “dot” samples produced by “one-pot” thermal carbonization of organic precursors are also popular in the literature. These carbonization-produced samples may contain nano-carbon domains embedded in organic matters from the precursors that survived the thermal processing, which may be considered and denoted as “nano-carbon/organic hybrids”. Recent experimental evidence indicated that the two different kinds of dot samples are largely divergent in their photo-induced antibacterial functions. In this work, three representative carbonization-produced samples from the precursor of citric acid–oligomeric polyethylenimine mixture with processing conditions of 200 °C for 3 h (CS200), 330 °C for 6 h (CS330), and microwave heating (CSMT) were compared with the classically synthesized CDots on their photo-induced antiviral activities. The results suggest major divergences in the activities between the different samples. Interestingly, CSMT also exhibited significant differences between antibacterial and antiviral activities. The mechanistic origins of the divergences were explored, with the results of different antimicrobial activities among the hybrid samples rationalized in terms of the degree of carbonization in the sample production and the different sample structural and morphological characteristics. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; (, ACS Nano)
    A major challenge in the “bottom-up” solvothermal synthesis of carbon dots (CDs) is the removal of small-molecule byproducts, noncarbonized polyamides, or other impurities that confound the optical properties. In previously reported benzene diamine-based CDs, the observed fluorescence signal already has been shown to arise from free small molecules, not from nanosized carbonized dots. Here we have unambiguously identified the small-molecule species in the synthesis of CDs starting with several isomers of benzene diamine by directly matching their NMR, mass spectrometry, and optical data with commercially available small organic molecules. By combining dialysis and chromatography, we have sufficiently purified the CD reaction mixtures to measure the CD size by TEM and STM, elemental composition, optical absorption and emission, and single-particle blinking dynamics. The results can be rationalized by electronic structure calculations on small model CDs. Our results conclusively show that the purified benzene diamine-based CDs do not emit red fluorescence, so the quest for full-spectrum fluorescence from isomers of a single precursor molecule remains open. 
    more » « less
  5. ; ; ; ; ; ; ; (, Small)
    Abstract Carbon dots are defined as small carbon nanoparticles with effective surface passivation via organic functionalization. The definition is literally a description of what carbon dots are originally found for the functionalized carbon nanoparticles displaying bright and colorful fluorescence emissions, mirroring those from similarly functionalized defects in carbon nanotubes. In literature more popular than classical carbon dots are the diverse variety of dot samples from “one‐pot” carbonization of organic precursors. On the two different kinds of samples from the different synthetic approaches, namely, the classical carbon dots versus those from the carbonization method, highlighted in this article are their shared properties and apparent divergences, including also explorations of the relevant sample structural and mechanistic origins for the shared properties and divergences. Echoing the growing evidence and concerns in the carbon dots research community on the major presence of organic molecular dyes/chromophores in carbonization produced dot samples, demonstrated and discussed in this article are some representative cases of dominating spectroscopic interferences due to the organic dye contamination that have led to unfound claims and erroneous conclusions. Mitigation strategies to address the contamination issues, including especially the use of more vigorous processing conditions in the carbonization synthesis, are proposed and justified. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email