Heterogeneous catalysis in continuous flow microreactors: A review of methods and applications

Abstract Over the past two decades, microreactor technology has evolved to become a crucial component in the development of process intensification. Microreactors have helped to minimize reagent consumption and energy waste due to their small dimensions, which in most cases do not exceed 1 mm in at least one dimension. The small volume of microreactors enables safe handling of even hazardous or highly exothermic reactions while facilitating fast and easy parameter screening. As a consequence of the small size, the ratio of surface area to volume is much higher than in conventional reactors. This in turn affects other properties such as the flow regime, and mass and heat transfer. Because high pressure and temperature can be handled much easier at a very small scale, microreactors unlock new process windows. If a catalyst is deposited inside the microreactor in the form of a thin coating or a monolith, these devices may have great prospects in heterogeneous catalysis spanning from petrochemical to pharmaceutical applications. In this tutorial review, different methodologies to immobilize heterogeneous catalysts in microreactor structures have been collected, and applications for process development, data generation, and synthesis in continuous flow have been critically assessed.

[1]  Stephan Laue,et al.  Experience with Scale-Up of Low-Temperature Organometallic Reactions in Continuous Flow , 2016 .

[2]  T. A. Nijhuis,et al.  The application of palladium and zeolite incorporated chip-based microreactors , 2016 .

[3]  P. Claus,et al.  The influence of real structure of gold catalysts in the partial hydrogenation of acrolein , 2003 .

[4]  C. Wiles,et al.  Continuous process technology: a tool for sustainable production , 2014 .

[5]  Ryan L. Hartman,et al.  Packed-bed microreactors for understanding of the dissolution kinetics and mechanisms of asphaltenes in xylenes , 2016 .

[6]  José L. Fernández,et al.  Microreactor with silver-loaded metal-organic framework films for gas-phase reactions , 2017 .

[7]  A. Kirschning,et al.  Manufacturing and construction of PASSflow flow reactors and their utilization in Suzuki-Miyaura cross-coupling reactions , 2005 .

[8]  N G Wilson,et al.  Microfabricated reactors for on-chip heterogeneous catalysis. , 2001, The Analyst.

[9]  T. Akita,et al.  Hydrogenation of 1,3-butadiene and of crotonaldehyde over highly dispersed Au catalysts , 2002 .

[10]  J. Clark,et al.  Base catalysts immobilised on silica coated reactor walls for use in continuous flow systems , 2004 .

[11]  T. Suzuki,et al.  Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors , 2013, Beilstein journal of organic chemistry.

[12]  V. Meille,et al.  Review on methods to deposit catalysts on structured surfaces , 2006 .

[13]  P. Pfeifer,et al.  Preparation and Performance of a Catalyst-Coated Stacked Foil Microreactor for the Methanol Synthesis , 2010 .

[14]  Martin D. Johnson,et al.  Operation Strategy Development for Grignard Reaction in a Continuous Stirred Tank Reactor , 2016 .

[15]  E. Rebrov,et al.  A kinetic study of the liquid-phase hydrogenation of citral on Au/TiO2 and Pt–Sn/TiO2 thin films in capillary microreactors , 2011 .

[16]  Zijian Zheng,et al.  Monolithic hierarchical gold sponges for efficient and stable catalysis in a continuous-flow microreactor , 2017 .

[17]  Paul Watts,et al.  Recent advances in synthetic micro reaction technology. , 2007, Chemical communications.

[18]  C. Wiles,et al.  Continuous flow reactors: a perspective , 2012 .

[19]  F. Carniato,et al.  Niobium metallocenes deposited onto mesoporous silica via dry impregnation as catalysts for selective epoxidation of alkenes , 2013 .

[20]  E. Hilder,et al.  Macroporous monolith supports for continuous flow capillary microreactors , 2006 .

[21]  Riccardo Porta,et al.  Flow Chemistry: Recent Developments in the Synthesis of Pharmaceutical Products , 2016 .

[22]  Jurriaan Huskens,et al.  Supported Catalysis in Continuous-Flow Microreactors , 2015 .

[23]  Ryan L Hartman,et al.  Microchemical systems for continuous-flow synthesis. , 2009, Lab on a chip.

[24]  S. Trasatti,et al.  γ-Alumina as a Support for Catalysts: A Review of Fundamental Aspects , 2005 .

[25]  Y. Uozumi,et al.  Catalytic asymmetric allylic alkylation in water with a recyclable amphiphilic resin-supported P,N-chelating palladium complex. , 2001, Journal of the American Chemical Society.

[26]  H. Pennemann,et al.  Optimization of Wash-Coating Slurries as Catalyst Carrier for Screen Printing into Microstructured Reactors , 2013 .

[27]  J. Long,et al.  Introduction to metal-organic frameworks. , 2012, Chemical reviews.

[28]  D. Pirozzi,et al.  In-situ sol-gel modification strategies to develop a monolith continuous microreactor for enzymatic green reactions , 2016 .

[29]  Ronghua Ding,et al.  Bromination of Aromatic Compounds using Bromine in a Microreactor , 2016 .

[30]  Catalysts Immobilized on Organic Polymeric Monolithic Supports: From Molecular Heterogeneous Catalysis to Biocatalysis , 2012 .

[31]  Dominique M. Roberge,et al.  Liquid–liquid flow regimes and mass transfer in various micro-reactors , 2016 .

[32]  J. Clark,et al.  A novel highly active biomaterial supported palladium catalyst , 2005 .

[33]  T. Tuziuti,et al.  Ultrasonic cavitation in microspace. , 2004, Chemical communications.

[34]  T. Horiuchi,et al.  A novel alumina catalyst support with high thermal stability derived from silica-modified alumina aerogel , 1999 .

[35]  Kazuki Nakanishi,et al.  Phase separation in silica sol-gel system containing polyacrylic acid I. Gel formaation behavior and effect of solvent composition , 1992 .

[36]  G. Tranmer,et al.  The utilization of copper flow reactors in organic synthesis. , 2015, Chemical communications.

[37]  B. Enger,et al.  Modified alumina as catalyst support for cobalt in the Fischer–Tropsch synthesis , 2011 .

[38]  Y. Wang,et al.  Facile immobilization of Ag nanoparticles on microchannel walls in microreactors for catalytic applications , 2017 .

[39]  T. Ohmori,et al.  Enzymatic reactions inside a microreactor with a mesoporous silica catalyst support layer , 2009 .

[40]  Christopher A. Hone,et al.  The Use of Molecular Oxygen in Pharmaceutical Manufacturing: Is Flow the Way to Go? , 2017, ChemSusChem.

[41]  Naoki Toshima,et al.  Polymer-Protected Ni/Pd Bimetallic Nano-Clusters: Preparation, Characterization and Catalysis for Hydrogenation of Nitrobenzene , 1999 .

[42]  Paul Watts,et al.  The application of micro reactors for organic synthesis. , 2005, Chemical Society reviews.

[43]  U. Hanefeld,et al.  MsAcT in siliceous monolithic microreactors enables quantitative ester synthesis in water , 2016 .

[44]  W. Yuan,et al.  Propylene epoxidation in a microreactor with electric heating , 2005 .

[45]  Volker Hessel,et al.  Novel Process Windows: Innovative Gates to Intensified and Sustainable Chemical Processes , 2015 .

[46]  Ferdi Schüth,et al.  The Controlled Oxidation of Hydrogen from an Explosive Mixture of Gases Using a Microstructured Reactor/Heat Exchanger and Pt/Al2O3 Catalyst , 2000 .

[47]  María José Nieves-Remacha,et al.  Gas–Liquid Flow and Mass Transfer in an Advanced-Flow Reactor , 2013 .

[48]  T. Hibiki,et al.  Some characteristics of air-water two-phase flow in small diameter vertical tubes , 1996 .

[49]  Maw‐Ling Wang,et al.  Kinetics for dichlorocyclopropanation of 1,7-octadiene under the influence of ultrasound assisted phase-transfer catalysis conditions , 2007 .

[50]  A. Cavazzini,et al.  A monolithic 5-(pyrrolidin-2-yl)tetrazole flow microreactor for the asymmetric aldol reaction in water–ethanol solvent , 2016 .

[51]  Takehiko Kitamori,et al.  A Microfluidic Device for Conducting Gas-Liquid-Solid Hydrogenation Reactions , 2004, Science.

[52]  C. Oliver Kappe,et al.  Continuous flow generation and reactions of anhydrous diazomethane using a Teflon AF-2400 tube-in-tube reactor. , 2013, Organic letters.

[53]  Volker Hessel,et al.  Lipase-Based Biocatalytic Flow Process in a Packed-Bed Microreactor , 2013 .

[54]  Holger Löwe,et al.  Review on patents in microreactor and micro process engineering , 2008 .

[55]  M. Fichtner,et al.  Process of Applying Al2O3 Coatings in Microchannels of Completely Manufactured Microstructured Reactors , 2002 .

[56]  Cara E. Brocklehurst,et al.  Nitration Chemistry in Continuous Flow using Fuming Nitric Acid in a Commercially Available Flow Reactor , 2011 .

[57]  L. Kiwi-Minsker,et al.  Compact string reactor for autothermal hydrogen production , 2007 .

[58]  Edmund G Seebauer,et al.  Porous anodic alumina optimized as a catalyst support for microreactors , 2004 .

[59]  Gunther Kolb,et al.  Propane steam reforming in micro-channels—results from catalyst screening and optimisation , 2004 .

[60]  K. Mae,et al.  Preparation and Control of the Size Distribution of Zirconia Nanoparticles in a Concentric‐Axle Dual‐Pipe Microreactor , 2013 .

[61]  U. Lafont,et al.  Mesoporous silica films as catalyst support for microstructured reactors: preparation and characterization , 2008 .

[62]  Sang Shin Park,et al.  Micro-channel reactor for steam reforming of methanol , 2007 .

[63]  Pascal Giorgi,et al.  Selective Oxidation of Activated Alcohols by Supported Gold Nanoparticles under an Atmospheric Pressure of O2: Batch and Continuous‐Flow Studies , 2017 .

[64]  Akira Igarashi,et al.  A miniaturized methanol reformer with Si-based microreactor for a small PEMFC , 2006 .

[65]  O. Muraza,et al.  Enhancement of the stability of microporous silica films in non-aqueous solvents at elevated temperature , 2009 .

[66]  G. Ertl,et al.  Handbook of Heterogeneous Catalysis , 1997 .

[67]  Flavien Susanne,et al.  Continuous flow synthesis. A pharma perspective. , 2012, Journal of medicinal chemistry.

[68]  Shinji Hasebe,et al.  Design of a Numbering-up System of Monolithic Microreactors and Its Application to Synthesis of a Key Intermediate of Valsartan , 2016 .

[69]  Gjergji Shore,et al.  Catalysis in capillaries by Pd thin films using microwave-assisted continuous-flow organic synthesis (MACOS). , 2006, Angewandte Chemie.

[70]  Ryan L. Hartman,et al.  Deciding whether to go with the flow: evaluating the merits of flow reactors for synthesis. , 2011, Angewandte Chemie.

[71]  Gjergji Shore,et al.  Propargyl amine synthesis catalysed by gold and copper thin films by using microwave-assisted continuous-flow organic synthesis (MACOS). , 2010, Chemistry.

[72]  Tom McCreedy,et al.  On-chip catalysis using a lithographically fabricated glass microreactor—the dehydration of alcohols using sulfated zirconia , 2000 .

[73]  G. Huber,et al.  Aqueous-phase reforming of ethylene glycol on silica-supported metal catalysts , 2003 .

[74]  C. Len,et al.  Silica-supported palladium: Sustainable catalysts for cross-coupling reactions , 2009 .

[75]  Christopher G. Frost,et al.  Heterogeneous catalytic synthesis using microreactor technology , 2010 .

[76]  Steven V. Ley,et al.  Hydrogenation in flow: Homogeneous and heterogeneous catalysis using Teflon AF-2400 to effect gas-liquid contact at elevated pressure†‡ , 2011 .

[77]  J. Santamaría,et al.  Preparation of Pt/ZSM-5 films on stainless steel microreactors , 2007 .

[78]  T. Mason,et al.  Applied Sonochemistry: The Uses of Power Ultrasound in Chemistry and Processing , 2002 .

[79]  C. Kappe,et al.  Microwave-assisted continuous flow synthesis on industrial scale , 2012 .

[80]  Norbert Kockmann Modular Equipment for Chemical Process Development and Small-Scale Production in Multipurpose Plants† , 2016 .

[81]  J. Levec,et al.  Kinetic Study of Methanol Synthesis over CuO/ZnO/Al2O3/V2O3 Catalyst Deposited on a Stainless Steel Surface , 2012 .

[82]  K. K. Hii,et al.  Aerobic oxidations in flow: opportunities for the fine chemicals and pharmaceuticals industries , 2016 .

[83]  Abhaya K. Datye,et al.  Wall coating of a CuO/ZnO/Al2O3 methanol steam reforming catalyst for micro-channel reformers , 2004 .

[84]  Hiroyuki Nakamura,et al.  A simple method of self assembled nano-particles deposition on the micro-capillary inner walls and the reactor application for photo-catalytic and enzyme reactions , 2004 .

[85]  R. Hayward,et al.  General Predictive Syntheses of Cubic, Hexagonal, and Lamellar Silica and Titania Mesostructured Thin Films§ , 2002 .

[86]  Jun Yue,et al.  Gas-liquid-liquid three-phase flow pattern and pressure drop in a microfluidic chip: similarities with gas-liquid/liquid-liquid flows. , 2014, Lab on a chip.

[87]  Thomas J Ober,et al.  Active mixing of complex fluids at the microscale , 2015, Proceedings of the National Academy of Sciences.

[88]  Leroy Cronin,et al.  3D-printed devices for continuous-flow organic chemistry , 2013, Beilstein journal of organic chemistry.

[89]  Paul Watts,et al.  Investigation of racemisation in peptide synthesis within a micro reactor. , 2002, Lab on a chip.

[90]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[91]  Yongqin Lv,et al.  Advances and recent trends in the field of monolithic columns for chromatography. , 2015, Analytical chemistry.

[92]  M. Buchmeiser Polymeric monolithic materials : Syntheses, properties, functionalization and applications , 2007 .

[93]  C. Brinker,et al.  Synthesis and characterization of highly ordered mesoporous thin films with -COOH terminated pore surfaces. , 2003, Chemical communications.

[94]  M.H.J.M. de Croon,et al.  Review of Patent Publications from 1990 to 2010 on Catalytic Coatings on Different Substrates, Including Microstructured Channels: Preparation, Deposition Techniques, Applications , 2012 .

[95]  K. Maresz,et al.  Titania-silica monolithic multichannel microreactors. Proof of concept and fabrication/structure/catalytic properties in the oxidation of 2,3,6-trimethylphenol , 2016 .

[96]  Volker Hessel,et al.  Packed-Bed Microreactor for Continuous-Flow Adipic Acid Synthesis from Cyclohexene and Hydrogen Peroxide , 2013 .

[97]  Anita Šalić,et al.  Application of microreactors in medicine and biomedicine , 2012 .

[98]  T. Dietrich,et al.  Production and Characteristics of Microreactors Made from Glass , 2005 .

[99]  Trevor Kletz,et al.  Learning from Accidents , 2001 .

[100]  Paul Watts,et al.  Green chemistry: synthesis in micro reactors , 2003 .

[101]  J. Yoshida,et al.  Integration of borylation of aryllithiums and Suzuki–Miyaura coupling using monolithic Pd catalyst , 2016 .

[102]  Jean-Claude Charpentier,et al.  Process Intensification by Miniaturization , 2005 .

[103]  Claudio Battilocchio,et al.  A machine-assisted flow synthesis of SR48692: a probe for the investigation of neurotensin receptor-1. , 2013, Chemistry.

[104]  Eamon Comer,et al.  A microreactor for microwave-assisted capillary (continuous flow) organic synthesis. , 2005, Journal of the American Chemical Society.

[105]  D. Roberge,et al.  Liquid–liquid mass transfer in a serpentine micro-reactor using various solvents , 2016 .

[106]  J. Khinast,et al.  Continuous Suzuki-Miyaura Reactions with Novel Ce-Sn-Pd Oxides and Integrated Crystallization as Continuous Downstream Protocol , 2016, Journal of Flow Chemistry.

[107]  M. Fichtner,et al.  Preparation of microstructure compatible porous supports by sol–gel synthesis for catalyst coatings , 2001 .

[108]  K. Jensen,et al.  Heterogeneous catalysis with continuous flow microreactors , 2012 .

[109]  Albert Renken,et al.  Micro-structured string-reactor for autothermal production of hydrogen , 2004 .

[110]  Shengyang Tao,et al.  Bio-inspired immobilization of metal oxides on monolithic microreactor for continuous Knoevenagel reaction. , 2016, Journal of colloid and interface science.

[111]  H. Löwe,et al.  Chemistry in microstructured reactors. , 2004, Angewandte Chemie.

[112]  Alex O Ibhadon,et al.  Novel synthesis of thick wall coatings of titania supported Bi poisoned Pd catalysts and application in selective hydrogenation of acetylene alcohols in capillary microreactors. , 2015, Lab on a chip.

[113]  V. Hessel,et al.  Passive micromixers for applications in the microreactor and μTAS fields , 2005 .

[114]  Volker Hessel,et al.  Recent changes in patenting behavior in microprocess technology and its possible use for gas-liquid reactions and the oxidation of glucose. , 2012, ChemSusChem.

[115]  Á. Berenguer-Murcia,et al.  Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports. , 2009, Lab on a chip.

[116]  L. Kiwi-Minsker,et al.  Microstructured catalytic reactors , 2010 .

[117]  David Sinton,et al.  Energy: the microfluidic frontier. , 2014, Lab on a chip.

[118]  A. Maguire,et al.  Taming hazardous chemistry in flow: the continuous processing of diazo and diazonium compounds. , 2015, Chemistry.

[119]  Hiroshi Yamada,et al.  Ultrasound-assisted capillary microreactor for aqueous–organic multiphase reactions , 2009 .

[120]  S. Y. Wong,et al.  On-demand continuous-flow production of pharmaceuticals in a compact, reconfigurable system , 2016, Science.

[121]  R. Luque,et al.  Liquid phase oxidation chemistry in continuous-flow microreactors. , 2016, Chemical Society reviews.

[122]  Freek Kapteijn,et al.  Preparation of monolithic catalysts , 2001 .

[123]  H. Fu,et al.  Superhydrophilic anatase TiO2 film with the micro- and nanometer-scale hierarchical surface structure , 2008 .

[124]  Z. Ismagilov,et al.  Synthesis and characterization of mesoporous silica thin films as a catalyst support on a titanium substrate , 2007 .

[125]  A. Wolf,et al.  Microreactors – A New Efficient Tool for Reactor Development , 2001 .

[126]  Thomas Schwalbe,et al.  Chemical synthesis in microreactors , 2002 .

[127]  E. Kumacheva,et al.  Polymerization in Microfluidic Reactors , 2010 .

[128]  M. Hursthouse,et al.  Silica-supported imine palladacycles - recyclable catalysts for the Suzuki reaction? , 2001 .

[129]  R. Luque,et al.  Aryl alkynylation versus alkyne homocoupling: unprecedented selectivity switch in Cu, phosphine and solvent-free heterogeneous Pd-catalysed couplings , 2005 .

[130]  C. Friend,et al.  Heterogeneous gold-based catalysis for green chemistry: low-temperature CO oxidation and propene oxidation. , 2007, Chemical reviews.

[131]  T. A. Nijhuis,et al.  Direct synthesis of propylene oxide in the liquid phase under mild conditions , 2016 .

[132]  T. Bieringer,et al.  Future Production Concepts in the Chemical Industry: Modular – Small‐Scale – Continuous , 2013 .

[133]  A. Kulkarni Continuous flow nitration in miniaturized devices , 2014, Beilstein journal of organic chemistry.

[134]  F. Kapteijn,et al.  Heterogeneously Catalyzed Continuous-Flow Hydrogenation Using Segmented Flow in Capillary Columns , 2011, ChemCatChem.

[135]  T. Tagawa,et al.  Ultrasound-assisted phase transfer catalysis in a capillary microreactor , 2009 .

[136]  Xiaohong Li,et al.  Pt nanoparticles supported on highly dispersed TiO2 coated on SBA-15 as an efficient and recyclable catalyst for liquid-phase hydrogenation , 2013 .

[137]  R. Luque,et al.  Nanocatalysis in continuous flow: supported iron oxide nanoparticles for the heterogeneous aerobic oxidation of benzyl alcohol , 2013 .

[138]  Tong Zhang,et al.  Continuous flow ZIF-8/NaA composite membrane microreactor for efficient Knoevenagel condensation , 2015 .

[139]  C. Amatore,et al.  Rates and mechanisms of oxidative addition to zerovalent palladium complexes generated in situ from mixtures of Pd0(dba)2 and triphenylphosphine , 1993 .

[140]  K. Nakanishi,et al.  Grafted Polymethylhydrosiloxane on Hierarchically Porous Silica Monoliths: A New Path to Monolith-Supported Palladium Nanoparticles for Continuous Flow Catalysis Applications. , 2017, ACS applied materials & interfaces.

[141]  S. Woo,et al.  A plate-type reactor coated with zirconia-sol and catalyst mixture for methanol steam-reforming , 2005 .

[142]  K. Nakanishi,et al.  Preparation of monolithic silica columns for high-performance liquid chromatography. , 2008, Journal of chromatography. A.

[143]  Kazuki Nakanishi,et al.  Phase Separation in Gelling Silica–Organic Polymer Solution: Systems Containing Poly(sodium styrenesulfonate) , 1991 .

[144]  G. Neri,et al.  Selective hydrogenation of α,β-unsaturated ketone to α,β-unsaturated alcohol on gold-supported iron oxide catalysts: Role of the support , 2005 .

[145]  Timothy Noël,et al.  Cross-coupling in flow. , 2011, Chemical Society reviews.

[146]  Xiaohong Wang,et al.  Preparation of ordered mesoporous TiO2 thin film and its application in methanol catalytic combustion , 2013 .

[147]  A. Datye,et al.  Coating of steam reforming catalysts in non-porous multi-channeled microreactors , 2007 .

[148]  D. Barrow,et al.  Effect of segmented fluid flow, sonication and phase transfer catalysis on biphasic reactions in capillary microreactors , 2008 .

[149]  J. J. Kim,et al.  Method of catalyst coating in micro-reactors for methanol steam reforming , 2007 .

[150]  Stefan Neuberg,et al.  Micro reactor hydrogen production from ethylene glycol reforming using Rh catalysts supported on CeO2 and La2O3 promoted α-Al2O3 , 2014 .

[151]  María José Nieves-Remacha,et al.  Hydrodynamics of Liquid–Liquid Dispersion in an Advanced-Flow Reactor , 2012 .

[152]  A. Puglisi,et al.  A chiral organocatalytic polymer-based monolithic reactor , 2014 .

[153]  K. Wilson,et al.  Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow , 2015 .

[154]  Marcus Baumann,et al.  The synthesis of active pharmaceutical ingredients (APIs) using continuous flow chemistry , 2015, Beilstein journal of organic chemistry.

[155]  Jaiwook Park,et al.  One-pot synthesis of recyclable palladium catalysts for hydrogenations and carbon–carbon coupling reactions , 2004 .

[156]  J. Nikelly Dynamically coated PLOT [porous layer open tubular] columns , 1973 .

[157]  J. Xuan,et al.  Efficient Fischer–Tropsch microreactor with innovative aluminizing pretreatment on stainless steel substrate for Co/Al2O3 catalyst coating , 2016 .

[158]  N. Cherkasov,et al.  Scale up study of capillary microreactors in solvent-free semihydrogenation of 2‐methyl‐3‐butyn‐2‐ol , 2016 .

[159]  R. Guijt,et al.  Palladium-mediated organic synthesis using porous polymer monolith formed in situ as a continuous catalyst support structure for application in microfluidic devices , 2009 .

[160]  Andrew R. Bogdan,et al.  The Use of Copper Flow Reactor Technology for the Continuous Synthesis of 1,4‐Disubstituted 1,2,3‐Triazoles , 2009 .

[161]  N. Cherkasov,et al.  Solvent-free semihydrogenation of acetylene alcohols in a capillary reactor coated with a Pd–Bi/TiO2 catalyst , 2016 .

[162]  Chang-Soo Kim,et al.  Development of microchannel methanol steam reformer , 2004 .

[163]  Jean M. J. Fréchet,et al.  Continuous rods of macroporous polymer as high-performance liquid chromatography separation media , 1992 .

[164]  F. Kapteijn,et al.  Metal–Organic Framework Capillary Microreactor for Application in Click Chemistry , 2016 .

[165]  F. Liguori,et al.  Green semi-hydrogenation of alkynes by Pd@borate monolith catalysts under continuous flow , 2014 .

[166]  Gunther Kolb,et al.  Detailed Characterization of Various Porous Alumina-Based Catalyst Coatings Within Microchannels and Their Testing for Methanol Steam Reforming , 2003 .

[167]  Klavs F. Jensen,et al.  Flow chemistry—Microreaction technology comes of age , 2017 .

[168]  G. Chuah,et al.  A wall-coated catalytic capillary microreactor for the direct formation of hydrogen peroxide , 2010 .

[169]  Frank J. Villani,et al.  Application of Microreactor Technology in Process Development , 2004 .

[170]  Shuj Kobayashi,et al.  Flow “Fine” Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods , 2015, Chemistry, an Asian journal.

[171]  S. Kuhn,et al.  Oxidation of cinnamyl alcohol using bimetallic Au–Pd/TiO2 catalysts: a deactivation study in a continuous flow packed bed microreactor , 2016 .

[172]  B. Carbonnier,et al.  Gold nanoparticles-supported histamine-grafted monolithic capillaries as efficient microreactors for flow-through reduction of nitro-containing compounds , 2017 .

[173]  J. C. Jansen,et al.  Method for the in situ preparation of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications , 2007 .

[174]  Galen D. Stucky,et al.  pH Sensing with mesoporous thin films , 2001 .

[175]  Á. Berenguer-Murcia,et al.  Control of the thickness of mesoporous titania films for application in multiphase catalytic microreactors , 2010 .

[176]  Qingbing Zeng Fabrication of Al2O3‐coated carbon fiber‐reinforced Al‐matrix composites , 1998 .

[177]  Jc Jaap Schouten,et al.  Selective Hydrogenation of 2-Methyl-3-butyne-2-ol in a Wall-Coated Capillary Microreactor with a Pd25Zn75/TiO2 Catalyst , 2009 .

[178]  Woo Y. Lee,et al.  Surface-selective infiltration of thin-film catalyst into microchannel reactors , 2005 .

[179]  Z. Zeng,et al.  Solid-phase microextraction using fused-silica fibers coated with sol-gel-derived hydroxy-crown ether. , 2001, Analytical chemistry.

[180]  W. Lindner,et al.  Development of reactive thiol-modified monolithic capillaries and in-column surface functionalization by radical addition of a chromatographic ligand for capillary electrochromatography. , 2004, Journal of chromatography. A.

[181]  T. Mason Ultrasound in synthetic organic chemistry , 1997 .

[182]  T. Wirth,et al.  Electrochemical Synthesis in Microreactors , 2015, Journal of Flow Chemistry.

[183]  A. Pohar,et al.  Laminar to Turbulent Transition and Heat Transfer in a Microreactor: Mathematical Modeling and Experiments , 2008 .

[184]  Jixue Li,et al.  A water-compatible, highly active and reusable PEG-coated mesoporous silica-supported palladium complex and its application in Suzuki coupling reactions. , 2006, Chemical communications.

[185]  T. A. Nijhuis,et al.  Direct Synthesis of Hydrogen Peroxide over Au‐Pd Catalyst—The Effect of Co‐Solvent Addition , 2015 .

[186]  K. Furton,et al.  Innovations in sol-gel microextraction phases for solvent-free sample preparation in analytical chemistry , 2013 .

[187]  Albert Renken,et al.  Microstructured reactors for catalytic reactions , 2005 .

[188]  F. Kapteijn,et al.  High performance monolithic catalysts for hydrogenation reactions , 2005 .

[189]  Martin J. Taylor,et al.  Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors. , 2016 .

[190]  J. Hayes,et al.  Sol-gel chemistry-based Ucon-coated columns for capillary electrophoresis. , 1997, Journal of chromatography. B, Biomedical sciences and applications.

[191]  A. C. van Veen,et al.  Wall coating optimization for microchannel reactors , 2007 .

[192]  S. Kuhn,et al.  Continuous Heterogeneously Catalyzed Oxidation of Benzyl Alcohol Using a Tube-in-Tube Membrane Microreactor , 2015 .