Active Catalytic Species Research Articles

Zirconium Phosphates and Phosphonates: Applications in Catalysis

This review covers recent advancements in the use of zirconium phosphates and phosphonates (ZrPs) as catalysts or catalyst supports for a variety of reactions, including biomass conversion, acid–base catalysis, hydrogenation, oxidation, and C-C coupling reactions, from 2015 to the present. The discussion emphasizes the intrinsic catalytic properties of ZrPs, focusing on how surface acidity, hydrophobic/hydrophilic balance, textural properties, and particle morphology influence their catalytic performance across various reactions. Additionally, this review thoroughly examines the use of ZrPs as supports for catalytic species, ranging from organometallic complexes and metal ions to noble metals and metal oxide nanoparticles. In these applications, ZrPs not only enhance the dispersion and stabilization of active catalytic species but also facilitate their recovery and reuse due to their robust immobilization on the solid support. This dual functionality underscores the importance of ZrPs in promoting efficient, selective, and sustainable catalytic processes, making them essential to the advancement of green chemistry.

Metal organic framework derived N, P co-doped carbon coated Mo2C-Co6Mo6C hetero-structural nano bowl for efficiency overall water splitting

It is still important and challenge to explore bifunctional electrocatalysts with high catalytic activity for overall water splitting. Constructing heterostructure catalysts can integrate catalytic active species with different function as well as modify the catalytic activity of single component. In this work, by rational designing ZnCoMo metal organic framework (MOF) as the precursor, we successfully prepare Mo2C-Co6Mo6C nano bowl and investigate its potential for full water splitting. Due to the co-existence of highly active catalytic species of Mo2C and Co6Mo6C, the large specific surface area induced by the evaporation of Zn during calcination process, and the nano bowl-like morphology that boosts mass transfer, the as prepared ZnCoMo-900 can catalyze both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) effectively. Especially, it exhibits small overpotentials of 250 and 100 mV for OER and HER at 10 mA cm−2, as well as good stability. In addition, a small cell voltage of 1.54 V was achieved for overall water splitting at 10 mA cm−2, surpassing that of RuO2+Pt/C catalyst. This work provides a feasible route for designing heterostructure catalysts for water splitting.

The Central Role of Oxo Clusters in Zirconium‐Based Esterification Catalysis

Oxo clusters are a unique link between oxide nanocrystals and Metal‐Organic Frameworks (MOFs), representing the limit of downscaling each of the respective crystals. Herein, the superior catalytic activity of clusters, compared to zirconium MOF UiO‐66 and nanocrystals is shown. Focus is on esterification reactions given their general importance in consumer products and the challenge of converting large substrates. Oxo clusters have a higher surface‐to‐volume ratio than nanocrystals, rendering them more active. For large substrates, for example, oleic acid, MOF UiO‐66 has negligible catalytic activity while clusters provide almost quantitative conversion, a fact we ascribe to limited diffusion of large substrates through the MOF pores. Clusters do not suffer from limited mass transfer and we also obtain high conversion in solvent‐free reactions with sterically hindered alcohols (hexanol, 2‐ethyl hexanol, benzyl alcohol, and neopentyl alcohol). The cluster catalyst can be recovered and shows identical activity when reused. The structural integrity of the cluster is confirmed using X‐ray total scattering and pair distribution function analysis. Moreover, when homogeneous zirconium alkoxides are used as catalysts, the same oxo cluster is retrieved, showing that oxo clusters are the active catalytic species, even in previously assumed homogeneously catalyzed reactions.

Pd Nanoparticle Supported on N‐Doped Carbon Derived from Sodium Alginate/Melamine Blends as Efficient Heterogeneous Catalyst for Heck Reactions

AbstractN‐doped porous carbon shows great potential in the field of heterogenous supports due to its high porosity, large surface area, rich active sites, and strong chelation with catalytic active metals species. Herein, we successfully prepared a novel N‐doped porous carbon derived from sodium alginate/melamine blends (SAMNC) with different mass ratio through a simple carbonization and activation process. Hierarchical porous structure of the derived N‐doped carbon has been confirmed with the SEM, TEM, and N2 adsorption characterization. After Na2PdCl4 solution impregnation and further reduction process, Pd0 nanoparticles have been uniformly immobilized on the SAMNC support to produce novel Pd@SAMNC catalyst. The optimal Pd@SAMNC‐0.6 possesses a high N content (5.13%), Pd content (5.90%), large BET specific surface area of 1884.5 m2·g−1. Positron annihilation lifetime spectroscopy (PALS) investigation of the porous carbon materials provided the sub‐nano level microporous information proofs of Pd@SAMNC‐0.6 had the capability to provide more active sites for reactions than commercial Pd supported on activated carbon (Pd@AC). Pd@SAMNC‐0.6 catalyst showed superior catalytic efficiency in Heck coupling reaction between aromatic halides and alkenes and can be recycled for 17 runs without significant decrease in catalytic efficiency.

Ru-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated γ-Lactams.

A highly efficient Ru-catalyzed asymmetric hydrogenation of α,β-unsaturated γ-lactams has been developed by using a C2-symmetric ruthenocenyl phosphine-oxazoline as the chiral ligand. This method achieves the enantioselective synthesis of chiral β-substituted γ-lactams in high yields and with excellent enantioselectivities (up to 99% yield with 99% ee). Mechanistic studies based on detailed control experiments and computational investigation revealed that the cationic Ru-complex acts as the active catalytic species; the protonation process of the oxa-π-allyl-Ru complex, which is formed by the migratory insertion of the C=C double bond to the Ru-H bond (the stereocontrolling step) followed by an isomerization process, is the rate-determining step, and the existence of PPh3 is crucial for the highly efficient catalytic behavior. The protocol provides a straightforward and practical pathway for the synthesis of key intermediates for several chiral drugs and bioactive compounds, particularly for the 150 kg-scale industrial production of Brivaracetam, an antiepileptic drug that shows 13-fold more potent binding to the synaptic vesicle protein 2A compared with the well-known Levetiracetam.

Interfacial Engineering of Mn Porphyrin/Au Electrodes for Identifying MnOx as the Active Species under Oxygen Evolution Reactions.

Understanding the influence of surface structural features at a molecular level is beneficial in guiding an electrode's mechanistic proposals for electrocatalytic reactions. The relationship between structural stability and catalytic activity significantly impacts reaction performance, even though atomistic knowledge of active sites remains a topic of discussion. In this context, this work presents scanning tunneling microscopy (STM) results for the highly ordered arrangement of manganese porphyrin molecules on a Au(111) surface; STM allows us to monitor active sites at a molecular level to focus on long-standing issues with the electrocatalytic process, especially the exact nature of the real active sites at the interfaces. After water oxidation, manganese porphyrin rapidly decomposes into active catalytic species as bright protrusions. These newly formed active species drastically lost catalytic activity, up to 82%, through only acid treatment, one of the oxide removal methods, not by deionized water and acetone treatments. STM results of the obviated active species on the Au surface by an acidic solution support the forfeited catalytic activity. In addition, it shows a 67% decrement in catalytic activity by adsorption of phosphonic acid, one of the oxide's preferred adsorption materials, compared to the pristine one. Based on these observations, we confirm that the newly formed active species, as water oxidation catalysts, mostly consist of manganese oxides. Notable findings of our work provide molecular evidence for the active sites of Au and modified Au electrodes that spur the future development of water oxidation catalysts.

Oxygenate-induced structural evolution of high-entropy electrocatalysts for multifunctional alcohol electrooxidation integrated with hydrogen production

High-entropy compounds have been emerging as promising candidates for electrolysis, yet their controllable electrosynthesis strategy remains a formidable challenge because of the ambiguous ionic interaction and codeposition mechanism. Herein, we report a oxygenates directionally induced electrodeposition strategy to construct high-entropy materials with amorphous features, on which the structural evolution from high-entropy phosphide to oxide is confirmed by introducing vanadate, thus realizing the simultaneous optimization of composition and structure. The representative P-CoNiMnWVOx shows excellent bifunctional catalytic performance toward alkaline hydrogen evolution reaction and ethanol oxidation reaction (EOR), with small potentials of -168 mV and 1.38 V at 100 mA cm-2, respectively. In situ spectroscopy illustrates that the electrochemical reconstruction of P-CoNiMnWVOx induces abundant Co-O species as the main catalytic active species for EOR and follows the conversion pathway of the C2 product. Theoretical calculations reveal the optimized electronic structure and adsorption free energy of reaction intermediates on P-CoNiMnWVOx, thereby resulting in a facilitated kinetic process. A membrane-free electrolyzer delivers both high Faradaic efficiencies of acetate and H2 over 95% and superior stability at100 mA cm-2 during 120 h electrolysis. In addition, the unique composition and structural advantages endow P-CoNiMnWVOx with multifunctional catalytic activity and realize multipathway electrosynthesis of formate-coupled hydrogen production.

Dynamic in situ reconstruction of NiSe2 promoted by interfacial Ce2(CO3)2O for enhanced water oxidation

Understanding and manipulating the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity. Herein, we present a synthesis of NiSe2-Ce2(CO3)2O heterostructure and demonstrate the efficacy of interfacial Ce2(CO3)2O in promoting the formation of catalytically active centers to improve oxygen evolution activity. In-situ Raman spectroscopy shows that incorporation of Ce2(CO3)2O into NiSe2 causes a cathodic shift of the Ni2+→Ni3+ transition potential. Operando electrochemical impedance spectroscopy reveals that strong electronic coupling at heterogeneous interface accelerates charge transfer process. Furthermore, density functional theory calculations suggest that actual catalytic active species of NiOOH transformed from NiSe2, which is coupled with Ce2(CO3)2O, can optimize electronic structure and decrease the free energy barriers toward fast oxygen evolution reaction (OER) kinetics. Consequently, the resultant NiSe2-Ce2(CO3)2O electrode exhibits remarkable electrocatalytic performance with low overpotentials (268/304 mV @ 50/100 mA cm−2) and excellent stability (50 mA cm−2 for 120 h) in the alkaline electrolyte. This work emphasizes the significance of modulating the dynamic changes in developing efficient electrocatalyst.

Metal immobilized in a USY zeolite-supported (4-CB)TPPB: A new strategy of enhanced stability for acetylene hydrochlorination

Palladium (Pd)-based catalysts supported by silicaluminate materials are potential as the efficient non-mercury catalyst for acetylene hydrochlorination, which is a necessary industrial reaction for producing vinyl chloride monomer. A new strategy was employed to improve Pd/USY zeolite catalysts taking advantage of 4-carboxybutyl triphenylphosphonium bromide ((4-CB)TPPB) for acetylene hydrochlorination. The most active catalyst (Pd@20(4-CB)TPPB/USY) with the 0.5 wt% Pd loadings and the 20 wt% (4-CB)TPPB additives could achieve a stable acetylene conversion of 99.9 % and the vinyl chloride selectivity of 99.7 % during more than 50 h, outperforming the Pd/USY catalyst. The additive of (4-CB)TPPB was preferential to stabilize the catalytic active Pd species, inhibit the Pd (II) reduction and change the surface acidic properties during the preparation process and reaction, hence restraining the carbon deposition. Density functional theory (DFT) calculations further indicate that (4-CB)TPPB additives could effectively enhance the adsorption energy of catalyst for reactants and the desorption energy of vinyl chloride monomer (VCM) products, thus inhibiting the carbon deposition for improving the catalytic performance of Pd/USY catalysts. These findings provide guidance for designing efficient Pd-based catalysts as well as their utilization for acetylene hydrochlorination.

Bicarbonate-binding catalysis for the enantioselective desymmetrization of keto sulfonium salts

Herein, an enantioselective desymmetrization of cyclic keto sulfonium salts through enantioselective deprotonation/ring opening process by anion-binding catalysis is presented. We report a squaramide/HCO3- complex as catalytic active species which is able to stereo-differentiate two enantiomeric protons, triggering the ring opening event taking advantage of the great tendency of sulfonium salts to act as leaving groups. Thus, this desymmetrization methodology give rise to β-methylsulfenylated sulfa-Michael addition type products with excellent yields and very good enantioselectivities. The bifunctional organocatalyst has been demonstrated to be capable of activating simultaneously the base and the keto sulfonium salt by DFT calculations and experimental proofs.

Efficient calcium sulfite oxidation treatment by a highly active iron-manganese bimetallic metal-organic frameworks (MOFs)

Calcium sulfite (CaSO3) oxidation is the key step in the resource utilization of flue gas desulfurization (FGD) ash waste. However, under natural conditions the oxidation rate of CaSO3 is very low, limiting its conversion into calcium sulfate, an acceptable product for construction material. This study was devoted to the investigation of the synthesis and performance of a bimetallic MOFs with potential catalytic activity, namely, Fe/Mn(BDC)(DMF,F) catalysts. A combination of techniques including SEM, EDS, XRD, FT-IR, etc. were used to characterize the catalysts. The excellent catalytic performance examined in a gas-liquid-solid three-phase oxidation system are due to the special flexible respiratory architecture and homogeneous distribution of active sites, which allows the reactants to fully contact with the catalyst. Mn incorporated in the backbone of the metal-organic framework significantly enriches the catalytic active species that participate in a radical chain reaction with activated SO32- as ·SO3-, which in turn generates the key radical ·SO5- that reacts with SO32- to form SO42-. In the presence of Fe/Mn(BDC)(DMF, F)-13, the oxidation ratio of CaSO3 could reach 90.71%, which is more than 30-fold compared to non-catalytic oxidation and almost 5 times the effects of the single metal Fe(BDC)(DMF, F) catalyst. In addition, the study of kinetics shows that the oxidation rate of Fe/Mn(BDC)(DMF,F)-13 can reach 0.042 mmol·L-1·s-1 with an apparent activation energy of 10.86 kJ/mol. The oxidation rate is mainly affected by reaction temperature, pH value, catalyst concentration, and air flow rate. This study provides a potentially sustainable way for utilization of CaSO3-containing desulfurization ash.

Convenient construction of electrocatalysts via combustion-assisted corrosion engineering for efficient water oxidation

Developing an efficient strategy for the universal synthesis of electrocatalysts is crucial for advancing the industrialization of water splitting, yet it remains a significant challenge. In this study, we propose combustion-assisted corrosion engineering as a rapid method to fabricate electrocatalysts for the oxygen evolution reaction (OER) within seconds. By utilizing a three-dimensional framework composed of nickel foam and the unique structure of the active species, we enable swift electrolyte diffusion and gas release. Consequently, the optimized S–NiO/NF exhibits remarkable OER catalytic activity, requiring a low overpotential of 236 mV to achieve a current density of 50 mA cm−2 in 1.0 M KOH solution. Notably, the reconfiguration during the OER process leads to the formation of actual catalytic active species, enhancing the number of active centers and thereby improving the catalyst's performance. This research presents a versatile method for industrially fabricating non-noble metal self-supporting electrodes with high efficiency, offering a practical solution for energy conversion and storage.

Co/SiO2 Catalyst for Methoxycarbonylation of Acetylene: On Catalytic Performance and Active Species.

Reppe carbonylation of acetylene is an atom-economic and non-petroleum approach to synthesize acrylic acid and acrylate esters, which are key intermediates in the textile, leather finishing, and polymer industries. In the present work, a noble metal-free Co@SiO2 catalyst was prepared and evaluated in the methoxycarbonylation reaction of acetylene. It was discovered that pretreatment of the catalyst by different reductants (i.e., C2H2, CO, H2, and syngas) greatly improved the catalytic activity, of which Co/SiO2-H2 demonstrated the best performance under conditions of 160 °C, 0.05 MPa C2H2, 4 MPa CO, and 1 h, affording a production rate of 4.38 gMA+MP gcat-1 h-1 for methyl acrylate (MA) and methyl propionate (MP) and 0.91 gDMS gcat-1 h-1 for dimethyl succinate (DMS), respectively. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectra of CO adsorption (CO-DRIFTS) measurements revealed that an H2 reduction decreased the size of the Co nanoparticles and promoted the formation of hollow architectures, leading to an increase in the metal surface area and CO adsorption on the catalyst. The hot filtration experiment confirmed that Co2(CO)8 was generated in situ during the reaction or at the pre-activation stage, which served as the genuine active species. Our work provides a facile and convenient approach to the in situ synthetization of Co2(CO)8 for a Reppe carbonylation reaction.

Enhanced degradation of carbamazepine in water over Fe3O4@ZIF-8 nanocomposites with persulfate or peroxymonosulfate as activator

In this work, the Fe3O4@ZIF-8 catalyst was prepared by combining Fe3O4 with ZIF-8 for degrading carbamazepine (CBZ) in water, using activated persulfate (PS) and peroxymonosulfate (PMS). We investigated the optimal catalysts and reaction conditions for using PS or PMS as activators by varying the pH, temperature, catalyst dosage, as well as the dosage of PS and PMS, respectively. The results demonstrated that the CBZ removal rate using Fe3O4@ZIF-8 reached 98.1% after 30 min with a mass ratio of Fe3O4 to ZIF-8 = 3:1, temperature = 40°C, catalyst dosage = 0.50 g·L−1, and PS dosage = 0.25 g·L−1, using pH = 3.0. Characterization results show due to the fact that the presence of ZIF-8 facilitates the dispersion of the catalytic active species Fe3O4, prevents the agglomeration of the active species, increases the number of active species, and improves the catalytic performance. Furthermore, radical quenching assay and electron paramagnetic resonance spectra successfully identified the main oxidizing components generated in the system, namely SO4•− and •OH.

Nickel-Catalyzed Three-Component Unsymmetrical Bis-Allylation of Alkynes with Alkenes: A Density Functional Theory Study.

Density functional theory (DFT) characterizations were employed to resolve the structural and energetic aspects and product selectivities along the mechanistic reaction paths of the nickel-catalyzed three-component unsymmetrical bis-allylation of alkynes with alkenes. Our putative mechanism initiated with the in situ generation of the active catalytic species [Ni(0)L2] (L = NHC) from its precursors [Ni(COD)2, NHC·HCl] to activate the alkyne and alkene substrates to form the final skipped trienes. This proceeds via the following five sequential steps: oxidative addition (OA), β-F elimination, ring-opening complexation, C-B cleavage and reductive elimination (RE). Both the OA and RE steps (with respective free energy barriers of 24.2 and 24.8 kcal·mol-1) contribute to the observed reaction rates, with the former being the selectivity-controlling step of the entire chemical transformation. Electrophilic/nucleophilic properties of selected substrates were accurately predicted through dual descriptors (based on Hirshfeld charges), with the chemo- and regio-selectivities being reasonably predicted and explained. Further distortion/interaction and interaction region indicator (IRI) analyses for key stationary points along reaction profiles indicate that the participation of the third component olefin (allylboronate) and tBuOK additive played a crucial role in facilitating the reaction and regenerating the active catalyst, ensuring smooth formation of the skipped triene product under a favorably low dosage of the Ni(COD)2 catalyst (5 mol%).

Insight into heterogeneous photo-Fenton degradation of naphthol by natural magnetite: Redundancy analysis and toxicity assessment

Magnetite is a ubiquitous iron mineral in nature and its iron ions are usually isomorphically substituted by Ti and V cations, which shows a high ability for degradation of organic contaminants via the photo-Fenton process. However, numerous reports pay more attention to the activity of synthetic magnetite rather than natural magnetite. Here, three types of natural magnetite (HG01, HG02, and GCL01) with different Ti and V contents were investigated from the perspective of the difference in structural property, catalytic activity, H2O2 decomposition, and reactive oxygen species generation. Structural characterization exhibited that the purity of natural magnetite obeyed the order: GCL01 > HG02 > HG01. HG01 contained the highest Ti content in the form of ilmenite, followed by HG02 and GCL01. Moreover, HG01 yielded the highest photo-Fenton catalytic activity with 99.5 % of naphthol degradation and 96.0 % of H2O2 decomposition after 60 min reaction. The superior activity of HG01 was attributed to the relatively high Ti and V content as demonstrated by redundancy analysis. Mechanistic investigation implied that the Ti and V in the octahedral sites of the magnetite surface can accelerate the electron transfer from Fe(III) to Fe(II), resulting in higher Fenton activity. Besides, ilmenite in HG01 enhanced naphthol degradation because H2O2 accelerated the separation of photoelectron-holes pairs to promote O2− production. Furthermore, as revealed by gas chromatography-mass spectrometry and the toxicity of identified products predicted by the ECOSAR model, the toxicity of naphthol can effectively reduce accompanied by the harmless products generated. The high reusability, low iron ions residual in water, harmless end products, and easily recycled with magnetic separation suggest that natural magnetite has a promising application prospect for wastewater purification.

High-performance oxygen evolution reaction via self-optimizing interface engineering with simultaneous activation of dual-sites of surface oxyhydroxides

Metal oxyhydroxides produced by the surface reconstruction were widely considered as active catalytic species in the oxygen evolution reaction (OER). However, simultaneous activation of metal sites in surface oxyhydroxides remains a great challenge. In this study, the interface self-activation strategy was utilized to simultaneously activate both the iron and nickel sites at the surface oxyhydroxides of (Fe,Ni)OOH-NiSe2 nano heterostructure. The OER activity was greatly boosted by the dual activation of active sites, resulting in an overpotential of 245 mV@100 mA cm−2 with a small Tafel slope of 44 mV dec−1. The finely constructed FeOOH-NiSe2 heterostructure was transformed into (Fe,Ni)OOH-NiSe2 through the formation of distinct bonds of M(Fe,Ni)-O-Se during the OER process, which was discovered through a combination of experimental studies with DFT calculations. A fast OER reaction dynamic was achieved due to the unique self-optimized interface structure which produced a dual synergistic effect between the interface structure and the active sites of Fe and Ni of oxyhydroxides, modulated the electronic structure and d band center of active sites, and increased the number of optimum active sites. This work paves a way to design high-performance electrocatalysts with multiple active sites for other electrochemical reactions.

In situ generation of oxyanions-decorated cobalt(nickel) oxyhydroxide catalyst with high corrosion resistance for stable and efficient seawater oxidation

The development of efficient and robust anode materials for stable alkaline seawater electrolysis is severely limited by chlorine evolution reaction and chloride corrosion. Here, the sulfur-doped cobalt-nickel bimetallic phosphides (CoNiPS) are specifically designed as a pre-catalyst for navigating a surface reconstruction to fabricate the anions (PO43− and SO42−)-decorated Co(Ni)OOH catalyst (R-CoNiPS) with exceptional durability and high activity for stable alkaline seawater oxidation (ASO). Various experiment techniques together with theoretical simulations both demonstrate that the in situ-generated PO43− and SO42− anions on catalyst surface can improve the oxygen evolution reaction (OER) activity, regulating and stabilizing the catalytic active species Co(Ni)OOH, as well as make a critical role in inhibiting the adsorption of chloride ions and extending the service life of electrode. Therefore, this R-CoNiPS electrode exhibits superb OER activity toward ASO and stands out among the non-precious ASO electrocatalysts reported recently, requiring low overpotentials of 420 and 440 mV to attain large current densities of 500 and 1000 mA cm−2 in an alkaline natural seawater electrolyte, respectively. Particularly, the catalyst displays a negligible chloride corrosion at room temperature during ASO operation (>200 h) at 500 mA cm−2. This work opens up a new viewpoint for designing high-activity and durable electrocatalysts for seawater electrolysis.

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate-Metal-Organic-Framework Architecture.

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson-Evans polyoxometalate clusters (POMs, MMo6O24, M = Rh/Pt) within NU-1000, a Zr-based metal-organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.

Flash Organometallic Catalysis Uncovered by Continuous Microfluidic Devices.

The flash organometallic catalysis is a new concept that refers to the study of fast and controlled organometallic catalytic reactions by using microfluidic devices. Flash reactions' kinetics (ms-s scale) is often ignored due to the lack of proper research tool in organometallic chemistry. The development of microfluidic systems offers the opportunity to discover under-studied mechanisms and new reactions. In this concept, the basic theory of kinetic measurement in a microreactor is briefly reviewed and then two examples on studying flash organometallic catalytic transformation are introduced. One example is the discovery of a highly active palladium catalytic species for Suzuki Coupling and the other example is the study of a neglected isomerization catalytic cycle with a time scale of seconds before isomerization-hydroformylation by customized microfluidic devices. The last part is summary and prospect of this new area. Customizing a microfluidic device with good engineering design for a target reaction supports flash reactions' kinetic experimentation and could become a general strategy in chemistry lab.