Operando spectroscopy
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Operando spectroscopy is an analytical methodology wherein the spectroscopic characterization of materials undergoing reaction is coupled ''simultaneously'' with measurement of
catalytic Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
activity and selectivity. The primary concern of this methodology is to establish structure-reactivity/selectivity relationships of catalysts and thereby yield information about mechanisms. Other uses include those in engineering improvements to existing catalytic materials and processes and in developing new ones.


Overview and terms

In the context of organometallic catalysis, an ''
in situ ''In situ'' (; often not italicized in English) is a Latin phrase that translates literally to "on site" or "in position." It can mean "locally", "on site", "on the premises", or "in place" to describe where an event takes place and is used in ...
'' reaction involves the real-time measurement of a catalytic process using techniques such as
mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...
,
NMR Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are perturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a ...
,
infrared spectroscopy Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or function ...
, and
gas chromatography Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, ...
to help gain insight into functionality of the catalyst. Approximately 90% of industrial precursor chemicals are synthesized using catalysts. Understanding the catalytic mechanism and active site is crucial to creating catalysts with optimal efficiency and maximal product yield. ''In situ'' reactor cell designs typically are incapable of pressure and temperature consistency required for true catalytic reaction studies, making these cells insufficient. Several spectroscopic techniques require
liquid helium Liquid helium is a physical state of helium at very low temperatures at standard atmospheric pressures. Liquid helium may show superfluidity. At standard pressure, the chemical element helium exists in a liquid form only at the extremely low temp ...
temperatures, making them inappropriate for real-world studies of catalytic processes. Therefore, the ''operando'' reaction method must involve ''in situ'' spectroscopic measurement techniques, but under ''true'' catalytic kinetic conditions. ''Operando'' (Latin for ''working'') spectroscopy refers to continuous spectra collection of a working catalyst, allowing for simultaneous evaluation of both structure and activity/selectivity of the catalyst.


History

The term ''operando'' first appeared in catalytic literature in 2002. It was coined by Miguel A. Bañares, who sought to name the methodology in a way that captured the idea of observing a functional material — in this case a catalyst — under actual ''working'', i.e. device operation, conditions. The first international congress on operando spectroscopy took place in Lunteren, Netherlands, in March 2003, followed by further conferences in 2006 (Toledo, Spain),2009 (Rostock, Germany), 2012 (Brookhaven, USA), and 2015 (Deauville, France)."4th International Congress on Operando Spectroscopy"
ps.bnl.gov
The name change from ''in situ'' to ''operando'' for the research field of spectroscopy of catalysts under working conditions was proposed at the Lunteren congress. The analytical principle of measuring the structure, property and function of a material, a component disassembled or as part of a device simultaneously under operation conditions is not restricted to catalysis and catalysts. Batteries and fuel cells have been subject to operando studies with respect to their electrochemical function.


Methodology

Operando spectroscopy is a class of methodology, rather than a specific spectroscopic technique such as FTIR or NMR. Operando spectroscopy is a logical technological progression in in situ studies. Catalyst scientists would ideally like to have a "motion picture" of each catalytic cycle, whereby the precise bond-making or bond-breaking events taking place at the active site are known; this would allow a visual model of the mechanism to be constructed. The ultimate goal is to determine the structure-activity relationship of the substrate-catalyst species of the ''same'' reaction. Having two experiments—the performing of a reaction plus the real-time spectral acquisition of the reaction mixture—on a single reaction facilitates a direct link between the structures of the catalyst and intermediates, and of the catalytic activity/selectivity. Although monitoring a catalytic process in situ can provide information relevant to catalytic function, it is difficult to establish a perfect correlation because of the current physical limitations of in situ reactor cells. Complications arise, for example, for gas phase reactions which require large void volumes, which make it difficult to homogenize heat and mass within the cell. The crux of a successful operando methodology, therefore, is related to the disparity between laboratory setups and industrial setups, i.e., the limitations of properly simulating the catalytic system as it proceeds in industry. The purpose of operando spectroscopy is to measure the catalytic changes that occur within the reactor during operation using time-resolved (and sometimes spatially-resolved) spectroscopy. ''Time-resolved'' spectroscopy theoretically monitor the formation and disappearance of intermediate species at the active site of the catalyst as bond are made and broken in real time. However, current operando instrumentation often only works in the second or subsecond time scale and therefore, only relative concentrations of intermediates can be assessed. ''Spatially resolved'' spectroscopy combines spectroscopy with microscopy to determine active sites of the catalyst studied and spectator species present in the reaction.


Cell design

Operando spectroscopy requires measurement of the catalyst under (ideally) real ''working conditions'', involving comparable temperature and pressure environments to those of industrially catalyzed reactions, but with a spectroscopic device inserted into the reaction vessel. The parameters of the reaction are then measured continuously during the reaction using the appropriate instrumentation, i.e., online
mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...
,
gas chromatography Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, ...
or IR/NMR spectroscopy. Operando instruments ''(in situ cells)'' must ideally allow for spectroscopic measurement under optimal reaction conditions. Most industrial catalysis reactions require excessive pressure and temperature conditions which subsequently degrades the quality of the spectra by lowering the resolution of signals. Currently many complications of this technique arise due to the reaction parameters and the cell design. The catalyst may interact with the components of the operando apparatus; open space in the cell can have an effect on the absorption spectra, and the presence of spectator species in the reaction may complicate analysis of the spectra. Continuing development of operando reaction-cell design is in line with working towards minimizing the need for compromise between optimal catalysis conditions and spectroscopy. http://dspace.library.uu.nl/bitstream/handle/1874/23445/weckhuysen_04_in_situspectroscopyofcatalysts.pdf These reactors must handle specific temperature and pressure requirements while still providing access for spectrometry. Other requirements considered when designing operando experiments include reagent and product flow rates, catalyst position, beam paths, and window positions and sizes. All of these factors must also be accounted for while designing operando experiments, as the spectroscopic techniques used may alter the reaction conditions. An example of this was reported by Tinnemans et al., which noted that local heating by a Raman laser can give spot temperatures exceeding 100 °C. Also, Meunier reports that when using DRIFTS, there is a noticeable temperature difference (on the order of hundreds of degrees) between the crucible core and the exposed surface of the catalyst due to losses caused by the IR-transparent windows necessary for analysis.


Raman spectroscopy

Raman spectroscopy Raman spectroscopy () (named after Indian physicist C. V. Raman) is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman sp ...
is one of the easiest methods to integrate into a heterogeneous operando experiment, as these reactions typically occur in the gas phase, so there is very low litter interference and good data can be obtained for the species on the catalytic surface. In order to use Raman, all that is required is to insert a small probe containing two optical fibers for excitation and detection. Pressure and heat complications are essentially negligible, due to the nature of the probe. Operando confocal Raman micro-spectroscopy has been applied to the study of fuel cell catalytic layers with flowing reactant streams and controlled temperature.


UV-vis spectroscopy

Operando UV-vis spectroscopy is particularly useful for many homogeneous catalytic reactions because organometallic species are often colored. Fiber-optical sensors allow monitoring of the consumption of reactants and production of product within the solution through absorption spectra. Gas consumption as well as pH and electrical conductivity can also be measured using fiber-optic sensors within an operando apparatus.


IR spectroscopy

One case study investigated the formation of gaseous intermediates in the decomposition of CCl in the presence of steam over LaO using
Fourier-transform infrared spectroscopy Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectra ...
. This experiment produced useful information about the reaction mechanism, active site orientation, and about which species compete for the active site.


X-ray diffraction

A case study by Beale et al. involved preparation of
iron phosphate Iron phosphate may refer to: * Iron(II) phosphate * Iron(III) phosphate Iron(III) phosphate, also ferric phosphate, is the inorganic compound with the formula Fe PO4. Several related materials are known, including four polymorphs of FePO4 and ...
s and bismuth molybdate catalysts from an
amorphous In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("wi ...
precursor gel. The study found that there were no intermediate phases in the reaction, and helped to determine kinetic and structural information. The article uses the dated term ''in-situ'', but the experiment uses, in essence, an operando method. Although x-ray diffraction does not count as a spectroscopy method, it is often being used as an operando method in various fields, including catalysis.


X-ray spectroscopy

X-ray spectroscopy X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray radiation. Characteristic X-ray spectroscopy When an electron from the inner shell of an atom is excited by the energy o ...
methods can be used for genuine operando analyses of catalysts and other functional materials. The redox dynamics of sulfur with Ni/GDC anode during
solid oxide fuel cell A solid oxide fuel cell (or SOFC) is an electrochemical conversion device that produces electricity directly from oxidizing a fuel. Fuel cells are characterized by their electrolyte material; the SOFC has a solid oxide or ceramic electrolyte. A ...
(SOFC) operation at mid- and low-range temperatures in an operando S K-edge
XANES X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra (XAS) of condensed matter due to the p ...
have been studied. Ni is a typical catalyst material for the
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
in high temperature SOFCs. The operando spectro-electrochemical cell for this high temperature gas-solid reaction study under electrochemical conditions was based on a typical high temperature heterogeneous catalysis cell, which was further equipped with electric terminals. Very early method development for operando studies on PEM-FC fuel cells was done by Haubold et al. at
Forschungszentrum Jülich Forschungszentrum Jülich (FZJ here for short) is a national research institution that pursues interdisciplinary research in the fields of energy, information, and bioeconomy. It operates research infrastructures with a focus on supercomputers. C ...
and HASYLAB. Specifically they developed
plexiglas Poly(methyl methacrylate) (PMMA) belongs to a group of materials called engineering plastics. It is a transparent thermoplastic. PMMA is also known as acrylic, acrylic glass, as well as by the trade names and brands Crylux, Plexiglas, Acrylite, ...
spectro-electrochemical cells for XANES,
EXAFS Extended X-ray absorption fine structure (EXAFS), along with X-ray absorption near edge structure (XANES), is a subset of X-ray absorption spectroscopy (XAS). Like other absorption spectroscopies, XAS techniques follow Beer's law. The X-ray ab ...
and
SAXS Small-angle X-ray scattering (SAXS) is a small-angle scattering technique by which nanoscale density differences in a sample can be quantified. This means that it can determine nanoparticle size distributions, resolve the size and shape of (monodis ...
and ASAXS studies with control of the electrochemical potential of the
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requ ...
. Under operation of the fuel cell they determined the change of the particle size of and oxidation state and shell formation of the
platinum Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver". Platinu ...
electrocatalyst An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst ...
. In contrast to the SOFC operation conditions, this was a PEM-FC study in liquid environment under ambient temperature. The same operando method is applied to battery research and yields information on the changes of the
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
of electrochemically active elements in a
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in whi ...
such as Mn via XANES, information on coronation shell and bond length via EXAFS, and information on microstructure changes during battery operation via ASAXS. Since lithium ion batteries are intercalation batteries, information on the chemistry and electronic structure going on in the bulk during operation are of interest. For this, soft x-ray information can be obtained using hard
X-ray Raman scattering X-ray Raman scattering (XRS) is non-resonant inelastic scattering of X-rays from core electrons. It is analogous to vibrational Raman scattering, which is a widely used tool in optical spectroscopy, with the difference being that the wavelengths ...
. Fixed energy methods (FEXRAV) have been developed and applied to the study of the catalytic cycle for the oxygen evolution reaction on iridium oxide. FEXRAV consists of recording the absorption coefficient at a fixed energy while varying at will the electrode potential in an electrochemical cell during the course of an electrochemical reaction. It allows to obtain a rapid screening of several systems under different experimental conditions (''e.g.'', nature of the electrolyte, potential window), preliminary to deeper XAS experiments. The soft X-Ray regime (''i.e.'' with photon energy < 1000 eV) can be profitably used for investigating heterogeneous solid-gas reaction. In this case, it is proved that XAS can be sensitive both to the gas phase and to the solid surface states.


Gas chromatography

One case study monitored the dehydrogenation of propane to propene using micro-GC. Reproducibility for the experiment was high. The study found that the catalyst (Cr/AlO) activity increased to a sustained maximum of 10% after 28 minutes — an industrially useful insight into the working stability of a catalyst.


Mass spectrometry

Use of mass spectrometry as a second component of an operando experiment allows for optical spectra to be obtained before obtaining a mass spectrum of the analytes.
Electrospray ionization Electrospray ionization (ESI) is a technique used in mass spectrometry to produce ions using an electrospray in which a high voltage is applied to a liquid to create an aerosol. It is especially useful in producing ions from macromolecules becaus ...
allows a wider range of substances to be analysed than other ionization methods, due to its ability to ionize samples without thermal degradation. In 2017, Prof. Frank Crespilho and coworks introduced a new approach to operando DEMS, aiming the enzyme activity evaluation by differential electrochemical mass spectrometry (DEMS). NAD-dependent alcohol dehydrogenase (ADH) enzymes for ethanol oxidation were investigated by DEMS. The broad mass spectra obtained under bioelectrochemical control and with unprecedented accuracy were used to provide new insight into the enzyme kinetics and mechanisms.


Impedance spectroscopy


Applications


Nanotechnology

Operando spectroscopy has become a vital tool for surface chemistry.
Nanotechnology Nanotechnology, also shortened to nanotech, is the use of matter on an atomic, molecular, and supramolecular scale for industrial purposes. The earliest, widespread description of nanotechnology referred to the particular technological goal o ...
, used in materials science, involves active catalytic sites on a reagent surface with at least one dimension in the nano-scale of approximately 1–100 nm. As particle size decreases, surface area increases. This results in a more reactive catalytic surface."Nanotechnology Introduction – What is nanotechnology?"
''Nanowerk''.
The reduced scale of these reactions affords several opportunities while presenting unique challenges; for example, due to the very small size of the crystals (sometimes <5 nm), any
X-ray crystallography X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
diffraction signal may be very weak. As catalysis is a surface process, one particular challenge in catalytic studies is resolving the typically weak spectroscopic signal of the catalytically active surface against that of the inactive bulk structure. Moving from the micro to the nano scale increases the surface to volume ratio of the particles, maximizing the signal of the surface relative to that of the bulk. Furthermore, as the scale of the reaction decreases towards nano scale, individual processes can be discerned that would otherwise be lost in the average signal of a bulk reaction composed of multiple coincident steps and species such as spectators, intermediates, and reactive sites.


Heterogeneous catalysis

Operando spectroscopy is widely applicable to
heterogeneous catalysis In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Ph ...
, which is largely used in industrial chemistry. An example of operando methodology to monitor heterogeneous catalysis is the dehydrogenation of propane with molybdenum catalysts commonly used in industrial petroleum. Mo/SiO and Mo/AlO were studied with an operando setup involving EPR/ UV-Vis, NMR/UV-Vis, and Raman. The study examined the solid molybdenum catalyst in real time. It was determined that the molybdenum catalyst exhibited propane dehydrogenation activity, but deactivated over time. The spectroscopic data showed that the most likely catalytic active state was in the production of propene. The deactivation of the catalyst was determined to be the result of coke formation and the irreversible formation of crystals, which were difficult to reduce back to . The dehydrogenation of propane can also be achieved with chromium catalysts, through the reduction of to .
Propylene Propylene, also known as propene, is an unsaturated organic compound with the chemical formula CH3CH=CH2. It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petrole ...
is one of the most important organic starting materials is used globally, particularly in the synthesis of various plastics. Therefore, the development of effective catalysts to produce propylene is of great interest.Polyethylene Glycol
wisegeek.com
Operando spectroscopy is of great value to the further research and development of such catalysts.


Homogeneous catalysis

Combining operando Raman, UV–Vis and ATR-IR is particularly useful for studying homogeneous catalysis in solution. Transition-metal complexes can perform catalytic oxidation reactions on organic molecules; however, much of the corresponding reaction pathways are still unclear. For example, an operando study of the oxidation of veratryl alcohol by salcomine catalyst at high pH determined that the initial oxidation of the two substrate molecules to aldehydes is followed by the reduction of molecular oxygen to water, and that the rate determining step is the detachment of the product. Understanding organometallic catalytic activity on organic molecules is incredibly valuable for the further development of material science and pharmaceuticals.


References

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