Raman spectroscopy is one of the major characterization methods employed over the last few decades as a nondestructive technique for the study of heterogeneous catalysts and related catalytic reactions. However, the promise of practical applicability on millimeter-sized catalyst bodies, such as extrudates, has not been fulfilled completely. Large fluorescence signals and the highly scattering nature of the extrudates often hamper its practical usage. Different approaches to overcome this problem were examined, including the use of time-resolved Raman spectroscopy (TRRS), spatially offset Raman spectroscopy (SORS), surface-enhanced Raman spectroscopy (SERS), and combinations of these techniques. This paper demonstrates that especially TRRS can provide chemical information at depth within catalyst bodies, overcoming fluorescence background signals and allowing for visualization of analytes at different depths. It also examines the application of time-resolved SERS within catalyst bodies to gain insight into localized activity. With these options a wider applicability of Raman spectroscopy for industrial catalysis research becomes within reach.
GeusJ.W.“Production of Supported Catalysts by Impregnation and (Viscous) Drying”. In: RegalbutoJ., editor. Chap. Catalyst Preparation Science and Engineering. Boca Raton, US: CRC Press, 2007. Pp. 341–372.
4.
WeckhuysenB.M.“Space and Time-Resolved Spectroscopy of Catalyst Bodies”. In: de JongK.P., editor. Synthesis of Solid Catalysts. Weinheim, Germany: Wiley-VCH, 2009. Pp. 201–216.
5.
IglesiaE.SoledS.BaumgartnerJ.“Synthesis and Catalytic Properties of Eggshell Cobalt Catalysts for the Fischer-Tropsch Synthesis”. J. Catal.1995. 153: 108–122.
6.
BartholomewC.H.“Mechanisms of catalyst deactivation”. Appl. Cat., A.2001. 212(1): 17–60.
7.
Espinosa-AlonsoL.BealeA.M.WeckhuysenB.M.“Profiling Physicochemical Changes within Catalyst Bodies during Preparation: New Insights from Invasive and Noninvasive Microspectroscopic Studies”. Acc. Chem. Res.2010. 43(9): 1279–1288.
8.
BealeA.M.JacquesS.D.M.WeckhuysenB.M.“Chemical imaging of catalytic solids with synchrotron radiation”. Chem. Soc. Rev.2010. 39: 4656–4672.
9.
LysovaA.A.KoptyugI.V.“Magnetic resonance imaging methods for in situ studies in heterogeneous catalysis”. Chem. Soc. Rev.2010. 39: 4585–4601.
10.
ZandbergenM.W.JacquesS.D.WeckhuysenB.M.BealeA.M.“Chemical Probing within Catalyst Bodies by Diagonal Offset Raman Spectroscopy”. Angew. Chem. Int. Ed.2012. 51(4): 957–960.
11.
BanaresM.A.“Operando methodology: combination of in situ spectroscopy and simultaneous activity measurements under catalytic reaction conditions”. Catal. Today.2005. 100: 71–77.
12.
BrucknerA.“Looking on Heterogeneous Catalytic Systems from Different Perspectives: Multitechnique Approaches as a New Challenge for In Situ Studies”. Catal. Rev. Sci. Eng.2003. 45(1): 97–150.
13.
WachsI.E.RobertsC.A.“Monitoring surface metal oxide catalytic active sites with Raman spectroscopy”. Chem. Soc. Rev.2010. 39: 5002–5017.
14.
Le RuE.C.EtchgoinP.G.“A quick overview of surface-enhanced Raman spectroscopy”. In: Principles of Surface-Enhanced Raman Spectroscopy and Related Plasmonic Effects. Amsterdam, The Netherlands: Elsevier, 2009. Pp. 1–25, Chap 1.
15.
McNayG.EustaceD.SmithW.E.FauldsK.GrahamD.“Surface-Enhanced Raman Scattering (SERS) and Surface-Enhanced Resonance Raman Scattering (SERRS): A Review of Applications”. Appl. Spectrosc.2011. 65(8): 825–837.
16.
MatousekP.EverallN.TowrieM.ParkerA.W.“Depth profiling in diffusely scattering media using Raman spectroscopy and picosecond Kerr gating”. Appl. Spectrosc.2005. 59(2): 200–205.
17.
MatousekP.TowrieM.StanleyA.ParkerA.W.“Efficient rejection of fluorescence from Raman spectra using picosecond Kerr gating”. Appl. Spectrosc.1999. 53(12): 1485–1489.
18.
MatousekP.ClarkI.P.DraperE.R.C.MorrisM.D.GoodshipA.E.EverallN.TowrieM.FinneyW.F.ParkerA.W.“Subsurface Probing in Diffusely Scattering Media Using Spatially Offset Raman Spectroscopy”. Appl. Spectrosc.2005. 59(4): 393–400.
19.
EfremovE.BuijsJ.B.GooijerC.ArieseF.“Fluorescence rejection in resonance Raman spectroscopy using a picosecond-gated intensified charge-coupled device camera”. Appl. Spectrosc.2007. 61(6): 571–578.
20.
ArieseF.MeuzelaarH.KerssensM.M.BuijsJ.B.GooijerC.“Picosecond Raman spectroscopy with a fast intensified CCD camera for depth analysis of diffusely scattering media”. Analyst.2009. 134(6): 1192–1197.
21.
KimH.KosudaK.M.Van DuyneR.P.StairP.C.“Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions”. Chem. Soc. Rev.2010. 39(12): 4820–44.
22.
MeyerS.A.Le RuE.C.EtchegoinP.G.“Quantifying Resonant Raman Cross Sections with SERS”. J. Phys. Chem. A.2010. 114: 5515–5519.
23.
LiJ.-F.LiS.-B.AnemaJ.R.YangZ.-L.HuangY.-F.DingY.WuY.-F.ZhuoX.-S.WuD.-Y.RenB.WangZ.-L.TianZ.-Q.“Synthesis and Characterization of Gold Nanoparticles Coated with Ultrathin and Chemically Inert Dielectric Shells for SHINERS Applications”. Appl. Spectrosc.2011. 65(6): 620–626.
24.
StoneN.FauldsK.GrahamD.MatousekP.“Prospects of deep Raman spectroscopy for noninvasive detection of conjugated surface-enhanced resonance Raman scattering nanoparticles buried within 25 mm of mammalian tissue”. Anal. Chem.2010. 82: 3969–3973.
YuenJ.M.ShahN.C.WalshJ.T.JrGlucksbergM.R.Van DuyneR.P.“Transcutaneous Glucose Sensing by Surface-Enhanced Spatially Offset Raman Spectroscopy in a Rat Model”. Anal. Chem.2010. 82(20): 8382–8385.
27.
Iping PettersonI.E.DvořákP.BuijsJ.GooijerC.ArieseF.“Time-resolved spatially offset Raman spectroscopy for depth analysis of diffusely scattering layers”. Analyst.2010. 135(12): 3255–3259.
28.
Iping PettersonI.E.Lopez-LopezM.García-RuizC.GooijerC.BuijsJ.B.ArieseF.“Noninvasive detection of concealed explosives: depth profiling through opaque plastics by time resolved Raman spectroscopy”. Anal. Chem.2011. 83: 8517–8523.
29.
CletusB.OldsW.IzakeE.L.SundarajooS.FredericksP.M.JaatinenE.“Combined time- and space-resolved Raman spectrometer for the non-invasive depth profiling of chemical hazards”. Anal. Bioanal. Chem.2012. 403(1): 255–263.
30.
van BroekhovenJ.A.MestersC.M.“Process for the preparation of styrene”. US Patent 20090062584. Filed 2008. Issued 2009.
31.
LangeJ.-P.OttenV.“Dehydration of phenyl-ethanol to styrene: zeolite catalysis under reactive distilliation”. J. Catal.2006. 238: 6–12.
32.
HarveyC.E.van Schrojenstein LantmanE.M.MankA.J.G.WeckhuysenB.M.“An Integrated AFM-Raman instrument for studying heterogeneous catalytic systems: a first showcase”. Chem. Commun.2012. 48: 1742–1744.
33.
McHughC.J.KennedyA.R.SmithW.E.GrahamD.“TNT stilbene derivatives as SERRS active species”. Analyst.2007. 132(10): 986–988.
FreunschtP.Van DuyneR.P.SchneiderS.“Surface-enhanced Raman spectroscopy of transstilbene adsorbed on platinum- or self-assembled monolayer-modified silver film over nanosphere surfaces”. Chem. Phys. Lett.1997. 281(12): 372–378.
36.
LeeP.MeiselD.“Adsorption and surface-enhanced Raman of dyes on silver and gold sols”. J. Phys. Chem.1982. 86: 3391–3395.
37.
EverallN.HahnT.MatousekP.ParkerA.W.TowrieM.“Photon migration in Raman spectroscopy”. Appl. Spectrosc.2004. 58(5): 591–597.
38.
MatousekP.MorrisM.D.EverallN.ClarkI.P.TowrieM.DraperE.GoodshipA.ParkerA.W.“Numerical simulations of subsurface probing in diffusely scattering media using spatially offset Raman spectroscopy”. Appl. Spectrosc.2005. 59(12): 1485–1492.
