evironmental spectroscopy techniques

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[email protected] | www.avantes.com Avantes BV Oude Apeldoornseweg 28 7333 NS Apeldoorn The Netherlands Tel. +31 313 670 170 Avantes USA 500 S. Arthur Ave., Unit 500 Louisville, CO 80027 Tel. +1 (303)-410-8668 Abstract Chemistry, as a science that is so universally applicable, has fields of study that are all over the map. These disparate studies in chemistry mean that researchers and chemists could be working in industries just as varied. But there are some shared techniques and technologies used by researchers and industrialists that span the chemistry gamut. UV/Vis Spectroscopy is one of the common tools in many chemist’s tool box. This versatile measurement technique has a secure place in the chem- istry lab. APPLICATION NOTE: EVIRONMENTAL SPECTROSCOPY Nanoparticles.” Image Courtesy of Oregon State University CC BY-SA 2.0 Techniques Absorbance Reflection Attentuated Total Reflection Raman Keywords Colloids Nanoparticles Nuclear Magnetic Resonance

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[email protected] | www.avantes.com

Avantes BV Oude Apeldoornseweg 287333 NS ApeldoornThe NetherlandsTel. +31 313 670 170

Avantes USA500 S. Arthur Ave., Unit 500Louisville, CO 80027Tel. +1 (303)-410-8668

Abstract

Chemistry, as a science that is so universally applicable, has fields of study that are all over the map. These disparate studies in chemistry mean that researchers and chemists could be working in industries just as varied. But there are some shared techniques and technologies used by researchers and industrialists that span the chemistry gamut.

UV/Vis Spectroscopy is one of the common tools in many chemist’s tool box. This versatile measurement technique has a secure place in the chem-istry lab.

APPLICATION NOTE: EVIRONMENTAL SPECTROSCOPY

“Nanoparticles.” Image Courtesy of Oregon State University CC BY-SA 2.0

Techniques• Absorbance• Reflection• Attentuated Total Reflection• Raman

Keywords• Colloids• Nanoparticles• Nuclear Magnetic Resonance

UV/Vis spectroscopy refers to absorption/reflection measurements performed in the ultraviolet and visible light spectrum. The Beer-Lambert law, which relates the attenuation of light to properties of the material the light is passing through, states that the absorbance of a sample is directly proportional to the concentration of the absorbing analyte. You can frequently see this axiom at work in analytical chemistry to quantify analytes, monitor processes and reactions, and detect certain organic com-pounds.Atmospheric ChemistryAtmospheric chemistry plays a central role in our understanding of the mechanisms of local climate conditions and factors into global radiative balance as well. Researchers study a class of compounds called Secondary Organic Aerosols (SOAs) which are the reactive products of gas-phase photooxidation of both naturally-occurring and man-made UV/Vis spectroscopy refers to absorption/reflection measurements performed in the ultraviolet and visible light spectrum. The Beer-Lambert law, which relates the attenuation of light to properties of the material the light is passing through, states that the absorbance of a sample is directly proportional to the concentration of the absorbing analyte. You can frequently see this axiom at work in analytical chemistry to quantify analytes, monitor processes and reactions, and detect certain organic com-pounds.Atmospheric ChemistryAtmospheric chemistry plays a central role in our understanding of the mecha-nisms of local climate conditions and fac-tors into global radiative balance as well. Researchers study a class of compounds

called Secondary Organic Aerosols (SOAs) which are the reactive products of gas-phase photooxidation of both naturally-occurring and man-made vola-tile organic compounds (VOCs). There have been many studies on the reaction mechanisms in the propagation of SOAs, Dr. Kun Li and a team of fellow research-ers from the Institute of Chemistry at the Chinese Academy of Sciences and the Beijing National Laboratory for Molecular Sciences looked more closely at the opti-cal properties of these aerosols under varying reactive conditions [1].The scattering and absorptive proper-

ties, the direct components of the refractive index are more dependent on the composi-tion of the aerosols than of the concentra-tion or particle size. Understanding the link between the chemical composition of aero-sol pollutants and their optical properties allows for a much more accurate estimate of the global radiative effects of localized reac-tive conditions.Dr. Li’s team’s work tested the optical prop-erties of SOA particles generated in a Teflon smog chamber in the lab from several differ-ent precursor compounds and under vary-ing NOx levels. Using the AvaSpec-2048L spectrometer, the particles were shown to be nonabsorbent at wavelength 532 nm. Retrieving Refractive Indices (RI) for each sample at that wavelength yielded values ranging from 1.38-1.59 depending on which precursor compound generated the SOA and under what concentration of NOx, but independent of the concentration of SOA or of particle size. Ultimately their work sug-gests that many environmental models may overestimate the Refractive Index, and in turn the global radiative effects.

Colloids and Nanoparticle Reactions

One area of study in Chemistry that has received a great deal of attention in recent years is Nanoparticles. These nano-scale particles are between 1 and 100 nanometers in size and are surrounded by an interfacial layer

of ions, organic and inorganic compounds which can react with other substances. Nanoparticles can exist as a powder or in a solid matrix, but are often found in colloidal form, dispersed in an aqueous solution or gel.Nano particles are formed by either break-ing down larger particles or by a controlled chemical reaction assembly process. These microscopic particles can be used for molec-ular tagging, DNA probes, gene therapy, and even cancer treatment. They can be found in consumer products such as sunscreens, anti-glare/non-scratch eyeglasses, anti-microbial or heat resistant coatings, and even in our food supply. The processes of chemical assembly of nanoparticles can be tempera-mental and the stability and reproducibility of a reaction is dependent on many factors including solution temperature and humid-ity, and the purity and concentration of the reagents. Any study of nanoparticles neces-sarily begins with their production and one of the most widely accepted means of reac-tion monitoring is UV/Vis spectroscopy.A group of researchers Kaunas University of Technology, Department of Physics, Kaunas Lithuania analyzed colloidal silver nanoparticles created via silver salt reduc-tion. The chemical reduction of the silver salt solution was monitored throughout the reaction process using the AvaSpec-2048L UV/Vis spectrometer in the wavelength rage 300-700 nm. Colloidal silver exhibits a wide absorption band from 350-550 nm with an absorption peak at 445 nm. As nanoparticles begin to form, absorption increases, then as the particles grow in size, the absorption peak shifts toward the red wavelengths.

Stabilization of the absorption peak indicates that new nanoparticles have ceased forming. The data collected during the reaction process also allowed the researchers to calcu-late average particle size [2].Another group of researchers from the School of Chemistry and Chemical

Engineering at the Beijing Institute of Technology studying Nano-Hydrogel Colloidal (NHC) array photonic crystals for

UV/Vis in the Spot Light

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APPLICATION NOTE: BIOMEDICAL FLUORESCENCE

Salt Lake City Smog

By Eltiempo10 [CC BY-SA 3.0), courtesy of Wikimedia Commons

Spectral Response of Humidity on Nano-Hydrogel Colloids

Image Courtesy of Beijing Insistute of Technology

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APPLICATION NOTE: BIOMEDICAL FLUORESCENCE

the detection of humidity, relay on UV/Vis spectroscopy during the precipitation polym-erization synthesis process of developing their NHCs. The novel design of this colloidal gel humidity sensor allows the water absorb-ing properties of this hydrogel to swell and change volume in response to environ-mental stimulus. As the particles swell, the change in size of the particle causes a shift of the absorption bands toward the red. This displays as a change in color visible to the naked eye and tunable, covering the full vis-ible wavelength range from 400-760 nm cor-

responding to a 20-99.9% range in humidity. These experiments, supported and verified using the AvaSpec-ULS2048-TEC spectrometer, may lead to new sensor technologies which can be applied to a variety of organic and inorganic molecular detection sensors [3].

While UV/Vis spectroscopy can be a powerful tool on its own, this technique is frequently used in combination with other measure-ment techniques. The use of complementary techniques can provide researchers with richer sample data than either technique can achieve on its own. Alternatively, these methods can serve as a check of accuracy, with data deviations between methods pin-pointing sampling discrepancies.

UV/Vis Spectroscopy with Attenu-ated Total Reflection (ATR)

Another spectroscopic technique that is frequently paired with UV/Vis spectroscopy is attenuated total reflectance (ATR). In ana-lytical chemistry, when with strongly light absorbing, or optically dense material, ATR techniques can yield data about a sample by exploiting the electromagnetic evanescent field. During ATR, a beam of IR light is passed through a crystal with a high refractive index. Once the sample is on contact with the crystal, the incidence beam reflects off the interior surface of the crystal in contact with the sample. An electromagnetic field generated by the vibrations of this reflection penetrate into the sample revealing a band of absorption where the evanescent wave is attenuated.Dr. Thomas Bürgi at the University of Geneva, Switzerland, Department of Physical Chemistry pairs ATR with UV/Vis absorbance measurements to study oxidation reactions at the point of catalytic interfaces at an in-depth molecular level. During experiments, Dr. Bürgi collected simultaneous and syn-chronized ATR and UV/Vis spectra. Changing reaction conditions yielded complemen-

tary information from the combination of measurement techniques. Attenuated total reflection (ATR) was used with the AvaSpec-ULS2048 spectrometer to identify dissolved reaction products, while UV/Vis spectroscopy was very sensitive to changes of the catalyst [4].

UV/Vis Spectroscopy with Attenuat-ed Total Reflection (ATR), and Raman

Studying the synthesis of mixed oxide catalyst precursors, Dr. Ursula Bentrup and a team of scientists at the Leibniz Institute of Catalysis at the University of Rostock used multiple methodologies during their experiments for a deeper understanding of how varying synthesis parameters affect the structure and crystallinity of the precur-sors and the performance of the resulting catalysts.The in-situ UV/Vis measurements were used in the monitoring of the chemical reactions to track the formation an extinction of reac-tant species. Paired with Raman, research-ers could track changes at an atomic scale revealing a gradual crystallinity change of Co2+ from octahedral to tetrahedral. Using the AvaSpec-ULS2048 spectrometer with a specialized ATR probe, researchers observed absorption bands for molybdenum at 838, 879, 930, 1442, and 1632 nm, as well as a nitrate band around 1338 nm become broader and more intense as precipitate for-mation increased. This combined method of investigation has high potential for real-time monitoring of complex reactions in liquid phase, including the precipitate of solids [5].

UV/Vis Spectroscopy with Nuclear Magnetic Resonance (NMR)

One technique that is often combined with UV/Vis Spectroscopy is Nuclear Magnetic Resonance. German researchers publishing in the journal Angewandte Chemie studied the efficacy of combined UVNMR methodol-ogy in reaction monitoring to gain insight into the acid-based chemistry of strongly hydrogen-bonded complexes in aprotic solu-tions [N*]. These slow reactions are very sen-sitive to concentration, temperature, and the solvent used. Using the AvaSpec-ULS2048 spectrometer for UV/Vis spectroscopy allowed the researchers to monitor reac-tion states through changes in the spectra surrounding the phenol group absorption bands found at 315 nm in low pH solutions and shifting to 400 nm in high pH solutions. Meanwhile, simultaneous use of NMR meth-ods yields insight into the hydrogen geom-etry of the reaction product [6].

Complementary Measurement Methods

Chemical Reaction courtesy of Pexels.com

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Chemistry touches so many aspects of our lives that you are guaranteed to find chemistry at the forefront of many advances and developments. And you can trust that Avantes will be right there as well. Avantes’

decades of experience in developing custom designed systems for chemistry applications means researchers count on us for reliability and ease of use. Contact a sales engineer today to learn about the Avantes Advantage.

Avantes, Your Partner In Chemistry

APPLICATION NOTE: BIOMEDICAL FLUORESCENCE

References1. Li, Kun, et al. “Optical properties of secondary organic aerosols generated by photooxidation of aromatic hydrocarbons.” Scientific

reports 4 (2014): 4922.2. Šileikaitė, Asta, et al. “Analysis of silver nanoparticles produced by chemical reduction of silver salt solution.” Mater. Sci 12.4 (2006):

1392-1320.3. Wang, Zhe, et al. “Self-assembly of a nano hydrogel colloidal array for the sensing of humidity.” RSC Advances 8.18 (2018): 9963-

9969.4. Bürgi, Thomas. “Combined in situ attenuated total reflection infrared and UV–vis spectroscopic study of alcohol oxidation over

Pd/Al2O3.” Journal of Catalysis 229.1 (2005): 55-63.5. Bentrup, Ursula, et al. “Linking simultaneous in situ WAXS/SAXS/Raman with Raman/ATR/UV–vis spectroscopy: comprehensive

insight into the synthesis of molybdate catalyst precursors.” Topics in Catalysis 52.10 (2009): 1350-1359.6. Tolstoy, Peter M., et al. “Combined NMR and UV/Vis spectroscopy in the solution state: study of the geometries of strong OHO

hydrogen bonds of phenols with carboxylic acids.” Angewandte Chemie International Edition 48.31 (2009): 5745-5747.

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