Ce travail a porté sur la conversion du méthane en hydrogène par les procédés de vaporeformage et reformage à sec, utilisant de nouvelles formulations de catalyseurs afins d'augmenter la sélectivité en produit désiré (H₂), de réduire la production du monoxyde de carbone (CO) et défavoriser la formation de coke. Deux familles de catalyseurs, à base de nickel et de ruthénium supportés par la cérine et/ou l'alumine, ont été évaluées dans ces réactions. Il a été montré que les catalyseurs à base de ruthénium supportés par l'alumine présente une bonne activité catalytique et une très bonne résistance au dépôt de coke dans les réactions de reformage du méthane. La cérine joue un rôle déterminant dans les catalyseurs à base de nickel en favorisant la dispersion de la phase active et évitant la formation des agglomérats. Parallèlement, une inhibition de la formation de coke est observée grâce aux propriétés redox du solide. Les travaux ont porté également sur l'amélioration de la formulation des catalyseurs monométalliques, et un catalyseur bimétallique (Ru-Ni/CeO₂-Al₂O₃) actif, sélectif et stable pour la production d'hydrogène à partir du méthane a été mis au point. L'ajout d'un deuxième métal en faible teneur (0,5%) aide à maintenir le Ni sous sa forme actif empêchant la formation de coke sur la surface du catalyseur. Pour les deux réactions étudiées, les excellentes performances obtenues proviennent essentiellement de l'ajustement des paramètres de réaction et les paramètres de préparation des catalyseurs, ce qui ouvre de réelles perspectives d'application industrielle. / This work has focused on the methane conversion by steam reforming and dry reforming processes, through new catalyst formulations in order to increase the selectivity of expected products (H₂), to reduce carbon monoxide production (CO) and to limit the coke formation. Two categories of catalysts were evaluated in these reactions : nickel-based catalysts and ruthenium-based catalysts supported by ceria and/or alumina. It has been reported that the ruthenium-based catalysts supported by alumina provide important catalytic activity and high resistance to coke deposition in the methane reforming reactions. Ceria played a determining role in the nickel-based catalysts by enhancing the active phase dispersion without agglomerates and coke formation. Works have also continued on the improvement of the monometallic catalyst and an active bimetallic catalyst (Ru-Ni/CeO₂-Al₂O₃), selective and stable in hydrogen production from methane has been developed. The addition of a second metal helps maintaining Ni in its active form, preventing the coke formation on the catalyst surface. For the two considered reactions, the excellent performance was largely due to the adjustment of the reactions and catalyst parameters offering a real potential industrial application.

Propylene is the second most important starting chemical in the petrochemical industry after ethylene. Unlike ethylene, propylene readily undergoes substitution reactions including polymerisation, oxidation, halogenation, hydrohalogenation, alkylation, hydration, oligomerization and hydroformylation, which lead to a wide variety of important downstream products. One of the principal uses of propylene is to produce key chemicals from selective oxidation. In 2016, the world annual production of propylene is about 94 million tonnes, and the global proportion used to produce selective oxidation product is over 18%. They constitute a key part of the chemical industry and contribute towards substantial economic benefits. The application of Ag based heterogeneous catalysts to selective propylene oxidation is a key factor in the synthesis of nearly all downstream chemicals, however billions of pounds are lost every year due to unplanned reactor shutdown, safety control and environment unfriendly emission control as a results of inefficiency catalytic selectivity and activity. Despite, both theoretical and experimental research works have been intensively involved, the fundamental reason leading to these effects are not yet well understood. The work presented in this thesis explores a range of novel modification techniques that alter the activity of Ag nanocatalysts for selective propylene oxidation, especially in propylene epoxidation. Particular focus is placed on developing surface modified Ag catalysts through morphology control, surface architecture engineering with another sublayer metal. Using a combination of modelling, novel and traditional materials characterisation methods, it is found that these modification result in some significant electronic and/or geometric alterations to the Ag nanoparticles surface. The Ag-Ag bond distance can be dramatically enlarged by exposing a high-index Ag surface or a core-shell structure with monolayer Ag shell. When interacting with molecular oxygen, the molecular oxygen adsorption and dissociation behaviour is sensitive to the geometric changes in Ag surface. This leads to an enhanced selectivity toward propylene epoxidation than combustion resulting from preventing a C-H bond cleavage. Finally, be creating atomically dispersed Ag on zeolite, a completely different interaction between molecular oxygen and single atom Ag were discovered comparing to on a extensive silver surface. This leads to the observation of an excitingly new propylene oxidation reaction producing ethanol and CO₂ resulting from C=C bond cleavage. Overall, the research presented within this thesis demonstrated a number of methods for the intelligent design of novel heterogeneous Ag catalysts with remarkable activity and selectivity toward specific selective propylene oxidation. These modification methods are believed to be potentially applicable to a wide range of other catalytic reactions.

Le catalyseur quatre voies est destiné à diminuer simultanément les émissions d’hydrocarbures, de monoxyde de carbone, d’oxydes d’azote et de suies par l’intermédiaire d’un seul monolithe catalytique. Plusieurs études sur ce type de catalyseur ont montré que la présence d’oxydes d’azote entraîne une diminution de la température d’oxydation des suies. Cependant, l’effet de la présence d’eau sur l’adsorption des oxydes d’azote n’est pas encore clair, surtout en présence de suies. Les travaux présentés dans ce manuscrit ont pour but de mettre en évidence l’influence de la présence d’eau et/ou de suies sur le fonctionnement de catalyseur «piège à NOx». Les résultats obtenus montrent que la présence d’eau entraîne une inhibition de la fonction oxydante du catalyseur, une diminution de la quantité de stockage des oxydes d’azote, et une inhibition de la formation des espèces adsorbées de surface. Ces phénomènes ont été attribués à la voix réactionnelle spécifique en présence d’eau associée à l’adsorption des oxydes d’azote. Les résultats obtenus sur le mélange noir de carbone et catalyseur montrent que la présence de noir de carbone induit une diminution de stockage des oxydes d’azote. De plus, cet effet se trouve plus important en contact fort. Les expériences réalisées sur l’adsorption des oxydes d’azote en présence simultanée de noir de carbone et d’eau ont montré un effet non cumulé de l’eau et du noir de carbone. Ce phénomène a été attribué à une compétition entre l’action de l’eau qui favorise la formation de nitrate de cœur à partir des nitrates faiblement liés et l’action du noir de carbone qui tend à déstabiliser les nitrates faiblement liés pour former les carbonates. / The four ways catalyst is used to decrease the emissions of hydrocarbon, carbon monoxide, nitrogen oxides and soot by a monolithic catalyst. Several researches on this type of catalyst have shown that the presence of nitrogen oxides involves a decrease of the soot oxidation temperature. However, the effect of the presence of water on the nitrogen oxides adsorption is not clear yet, especially with the presence of soot. The works presented in this manuscript are intended to study the influence of the presence of water or/and soot on the performance of the catalyst NOx trap. The results showed that the presence of water involves an inhibition of the oxidation function of catalyst, a decrease of the capacity of the NOx storage, and an inhibition of the formation of the surface adsorbed species. It is attributed to a special reactive way in the presence of water linked to the adsorption of nitrogen oxides. The results obtained on the mix of carbon black and catalyst showed that the presence of carbon black induce a decrease of the NOx storage capacity of catalyst. Besides, this effect was more important with a tight contact between carbon black and catalyst. The experiments realized on the adsorption of nitrogen oxides with the presence of carbon black and water simultaneously showed an effect not accumulated of the water and the carbon black. This phenomenon is attributed to a competition between the action of water which favors the formation of the bulk nitrate from the weak-linked nitrates and the action of carbon black which tend to destabilize the weak-linked nitrates to form the carbonates.

The theme of this thesis is the development of mononuclear Ru-based complexes that are capable of catalyzing the water oxidation (or O2-evolving) reaction, e.g. 2 H2O → O2 + 4 H+ + 4 e−. Several families of mononuclear Ru water oxidation catalysts were designed and prepared. They feature with anionic ancillary ligands that contain carboxylate or phenolate donors. The properties of the catalysts were investigated in various aspects including coordination geometry, electrochemical behavior, and ligand exchange. All catalysts showed outstanding catalytic activity towards water oxidation in the presence of cerium(IV) ammonium nitrate as a sacrificial oxidant. High-valent Ru intermediates involved in the reactions were characterized both experimentally and theoretically. The kinetics of catalytic water oxidation was examined based on one catalyst and a prevailing catalytic pathway was proposed. The catalytic cycle involved a sequence of oxidation steps from RuII−OH2 to RuV=O species and O−O bond formation via water-nucleophilic-attack to the RuV=O intermediate. By comparing properties and catalytic performance of Ru catalysts herein with that of previously reported examples, the effect of anionic ancillary ligands was clearly elucidated in the context of catalytic water oxidation. Aiming to further application in an envisaged artificial photosynthesis device, visible light-driven water oxidation was conducted and achieved primarily in a homogeneous three-component system containing catalyst, photosensitizer, and sacrificial electron acceptor. Moreover, one model Ru catalyst was successfully immobilized on ordinary glass carbon surface through a facile and widely applicable method. / <p>QC 20121112</p>

Despite the growing interest in heterogeneous polymerization catalysis, the majority of the polymerization catalysts used industrially are single-use entities that are left in the polymer product. Recoverable and recyclable polymerization catalysts have not reached the industrial utility of single-use catalysts because the catalyst and product separation have not become economical. The successful development of recyclable transition metal polymerization catalysts must take a rational design approach, hence academic and industrial researchers need to further expand the fundamental science and engineering of recyclable polymerization catalysis to gain an understanding of critical parameters that allow for the design of economically viable, recoverable solid polymerization catalysts. Unfortunately, the rapid development of Atom Transfer Radical Polymerization over the past 10 years has not resulted in its wide spread industrial practice. Numerous reports regarding the immobilization of transition metal ATRP catalysts, in attempts to increase its applicability, have extended the fundamentals of recyclable polymerization catalysis. However, for industrial viability, more research is required in the area of how the catalyst complex immobilization methodology and support structure affect the catalyst polymerization performance, regeneration, and recyclability. A comprehensive rational catalyst design approach of silica-immobilized ATRP catalyst was undertaken to answer these questions and are discussed here.

In this study, the wastewater generated from etching process of the Printed Circuit Board (PCB) was treated by a process including both acidification and coagulation/sedimentation and then followed by the catalytic wet air oxidation (CWAO) over different catalysts (either Pt/SiO2¡PAl2O3 or Pt¡PX/£^-Al2O3) process in series. Although the initial chemical oxygen demand (COD) concentration of the wastewater is as high as 7740-12700 mg/L, the effluent of the pretreatment process was measured to have COD value in ranges of 3050-4260 mg/L. Several re-action parameters, such as reaction temperatures (200-260¢J), oxygen partial pressures (0-3 MPa), and two kinds of catalysts were performed experimentally to investigate the COD reduction of the wastewater during the CWAO process. Both reaction temperature and variety of catalyst are found most effectively on the COD reduction. However, the effect of oxygen partial pressure on the COD reduction is just in little. Results showed that the COD reduction during the CWAO over the Pt¡PX/£^-Al2O3 catalyst process is the most significant, which with a tow-step re-action and both the two reactions do obey first-order reaction kinetics. A change from a higher reaction activity of the CWAO reaction to a slower one implies a decrease of the reaction rate. On basis of our experiments data, the effective operating conditions of CWAO for the COD reduction was observed to be at temperature of 260¢J under oxygen partial pressure of 2.0 MPa and at a retention time period of 60 min. The COD conversion was calculated as high as 75%; however, it could be enhanced up to 78% and 91%, respectively, when the CWAO was conducted in presence of the Pt/SiO2¡PAl2O3 and Pt¡PX/£^-Al2O3 catalysts, respectively. It can be seen that the organic compound of the wastewater was mineralized most completely (with a COD/TOC ratio of 3.7¡Ó0.2) after the CWAO over the Pt¡PX/£^-Al2O3 catalyst process. Furthermore, a higher COD/TOC ratio of 3.9¡Ó0.3 was achieved when the Pt/SiO2¡PAl2O3 catalyst was in presence of the CWAO process, and the primitive WAO process had the highest COD/TOC ratio of 4.8¡Ó0.4. The experimental data showed that both a higher reaction temperature (¡Ù260¢J) and an application of catalyst are more important factors for the min-eralization of the organic compound of the wastewater during the CWAO process. In our investigation, BOD5/COD ratio has been used to assess if the WAO and/or the CWAO process treatment yield products more amenable to biodegradation. The BOD5/COD ratio was 0.68-0.93 when the reaction temperature was above 220¢J and the retention time was as long as 60 min. Unfortunately, the BOD5/COD ratio of the effluent from the CWAO process came out a lower value (0.45-0.65) though it was under the same reaction conditions. It is probable that the biodegradable portion of the organic compounds of the wastewater were decomposed easier during the CWAO process than during the WAO process. In addition, it was found that the products of the wastewater was decomposed partially into CO2 and into some low molecular weigh acids, such as formic acid, acetic acid, propionic acid, etc. The activation energy with respect to COD was calculated to be 38.42 kJ/mole and 83 kJ/mole, respectively, for the first-step reaction and for the second-step reaction, respectively, of the WAO process. It was al-so calculated that the first-step reaction of the CWAO over the Pt/SiO2¡PAl2O3 catalyst process has activation energy of 18.25 kJ/mole and 25.76 kJ/mole is for the second-step reaction. However, 16.05 kJ/mole and 49.61 kJ/mole are calculated for the first-step and the sec-ond-step reactions, respectively, of the CWAO over the Pt¡PX/£^-Al2O3 catalyst process. It can be seen that the application of both the Pt/SiO2¡PAl2O3 and the Pt¡PX/£^-Al2O3 catalysts has a significant effect on reducing the activation energy of the WAO. It was observed that the total COD conversion of the wastewater is as high as 96% and the BOD5/COD ratio of the effluent has been en-hanced up to more than 0.6. The combination of both the CWAO over the Pt¡PX/£^-Al2O3 catalyst and the biological treatment is a promising tech-nique for the PCB¡¦s wastewater treatment to fit the wastewater control regulation in Taiwan, which requests the COD value of the wastewater discharged should be less than 120 mg/L.

Abstract Isopropyl alcohol¡]IPA¡^and toluene are extensively used in industry as solvents. They are all highly toxic to animals and humans. Accordingly, IPA and toluene are strongly associated with problems of VOCs. In first step catalytic incineration was adopted to decompose IPA and toluene in laboratory, and the second step for a pilot-scale regenerative catalytic oxidizer ¡]RCO¡^were adopted to decompose mixture VOCs in real soil herein. The screening test of catalytic activity and the influences of the operational parameters on IPA and toluene removal efficiencies were widely discussed through catalytic incinerations of IPA and toluene in laboratory. The more effective and cheaper catalysts through above discussions of catalytic incineration were selected. And they were utilized in an pilot scale RCO as follows to investigate their performance in VOCs oxidation and RCO operations in THC removal of contamination soils. The achievements of this study are summarized as follows: ¡]1¡^Cu/Mn and Cu/Co gravel catalytic incinerations of isopropyl alcohol The results demonstrated that 10 wt% Cu0.6Co0.4 catalyst was the most effective because the CO2 yield reached 95 % under the following operating conditions; a temperature of 425oC, an inlet IPA concentration of 2500 ppm, an oxygen concentration of 21%, and a space velocity of 13500 hr-1. Additionally, the stability test results indicated that the 10 wt% Cu0.6Co0.4 catalyst exhibited excellent stability at both low and high conversion of IPA. ¡]2¡^20% Cu/Mn aluminum oxide catalytic incinerations of toluene The conversion for toluene reached 95% when the Cu/Mn catalyst was used with a metal ratio of 1:1 and 20% loading at 350¢XC, an influent toluene concentration of 1000 ppm, oxygen concentration of 21%, a space velocity of 12000 hr-1, and relative humidity of 26%. The long-term test was proceeded for seven days at a constant influent toluene concentration of 1000 ppm, constant oxygen concentration of 21%, constant space velocity of 12000 hr-1 and constant relative humidity of 26%. The SEM results indicated the Cu/Mn catalyst was quite stable at 350¢J. ¡]3¡^RCO testing for a copper/manganese catalyst of gaseous toluene The Cu/Mn (20wt%) catalyst was selected as the best one, because it converted 95% of the toluene at 400¢J. The results also indicating that the Cu/Mn catalyst was quite stable at 400¢J. (4) RTO treatment of VOCs with SVE system The conversion for VOCs reached 80% at 900¢XC, an influent VOCs concentration of 450-2000 ppm and a gas flow rate of 0.5 m3/min.The Thermal Recovery Efficiency¡]TRE¡^was approximately 86-90% in a RTO operated at 800-900¢J. (5)RCO treatment of VOCs with SVE system¡]10 wt% Cu0.6Co0.4 gravel catalyst¡^ The 10 wt% Cu0.6Co0.4 gravel catalyst was the poverty active, because it converted 65% of the VOCs by SVE system operated at 650¢J. (6)RCO treatment of VOCs with SVE system¡]20% Cu/Mn aluminum oxide catalytst¡^ The 20% Cu/Mn aluminum oxide catalytic was the best choice, because it converted 95% of the VOCs at 650¢J, an influent VOCs concentration of 450-10000 ppm and a gas flow rate of 0.5-1.5 m3/min. The SEM results indicated that the conversion of VOCs decay did not clearly vary at 650¢J, also indicating that the Cu/Mn catalyst selected was quite stable. The TRE was approximately 90% in a RCO¡]20% Cu/Mn aluminum oxide catalytic¡^operated at 650¢J. (7)RCO treatment of VOCs with SVE system¡]20% Cu/Mn gravel catalytst¡^ The 20% Cu/Mn gravel catalytst was the best selection , because it converted 95% of the VOCs at 600¢J, an influent VOCs concentration of 450-10000 ppm and a gas flow rate of 0.5-1.5 m3/min. The SEM results indicated that the conversion of VOCs decay did not clearly vary at 600¢J, also indicating that the Cu/Mn catalyst selected was quite stable. The TRE was approximately 90% in a RCO¡]20% Cu/Mn gravel catalytic¡^operated at 600¢J.

In this work, carbonaceous deposits on spent HTFT catalysts were investigated. This research was required in order to better understand the observed loss in productivity observed in the industrial reactors, with the aim of improving the economy of the HTFT process. A host of complementary techniques were employed to systematically determine the composition of a typical catalyst recovered from a reactor. Spent HTFT catalysts are comprised of magnetite and a mixture of iron carbides as well as adsorbed hydrocarbon products (soft carbon) and hard carbon. Reaction initiates at the particle surface and along the promoter-rich grain boundaries toward the core of the grains. A partially reacted particle would therefore have a core-shell structure, with magnetite representing the unreacted region of the catalyst. The reacted region consists of a porous carbonaceous matrix with soft carbon and carbide crystallites nestled in this matrix. The hard carbonaceous species is a mixture of polymeric carbon and polycyclic aromatic hydrocarbons. The particle structure is linked to the sample preparation method and an alternative method yielding catalyst particle with uniformly distributed promoter elements could be beneficial. Investigating carbonaceous species is a complex process, and development of a fresh methodology would aid in the quest for insight into the nature of carbonaceous species in various systems. A new approach which entails a combination of the traditional techniques combined with MALDI-TOF MS enabled a deeper investigation. Additional aspects such as the molecular weight distributions along with known information about crystallinity and morphology of the catalyst provide a comprehensive study of carbonaceous material. Polymeric carbon and very large polycyclic aromatic hydrocarbons constitute hard carbon and can be observed with minimal sample preparation procedures. The evolution of the HTFT catalysts was investigated as a function of time-on-stream. This enabled us to study the effects of increasing amounts of hard carbon on the activity and the chemical and physical properties of the catalysts. The catalyst activity was found to decrease with increasing hard carbon content, although the effect of carbon deposition cannot be distinguished from phase transformation (oxidation) which occurs simultaneously. A method to quantify the amount of hard carbon, which progressively builds up on the catalyst, was demonstrated. This required a great deal of method development, which provides a platform for future investigations of these catalysts. Importantly, it allows predictions of the amounts of carbon that will be deposited after a certain reaction time. This allows more efficient regulation of catalyst replacement. The production of fine carbon-rich particles in the industrial reactor poses a major problem in the process. Carbon deposition leads to an increase in particle diameter with time on-stream. Permissible levels of hard carbon were identified, beyond which the mechanical strength of the catalyst particles deteriorate. This leads to break-up of the particles and therefore fines formation. The surface area and pore volume generally increase with progressive deposition of hard carbon, while the bulk density of the catalyst material exhibits a linear decrease with carbon build-up. A mechanism is proposed for hard carbon formation which apparently occurs through the dissociative adsorption of CO to form a carbon monolayer. This is followed by polymerisation of the carbon atoms. Meta-stable interstitial carbides are formed at the iron-carbon interface. Owing to a carbon concentration gradient between the top of the surface and the bottom of the metal or carbide particle, carbon diffusion across the crystal (carbide decomposition) and grows as a PAH molecule lifting the iron carbide away from the particle. As this corrosion process is intrinsic to iron-based catalysts, a catalyst that contains sulphur is proposed for future development.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16808号 / 工博第3529号 / 新制||工||1534(附属図書館) / 29483 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 杉野目 道紀, 教授 村上 正浩, 教授 吉田 潤一 / 学位規則第4条第1項該当

La catalyse constitue un élément clé en synthèse chimique et la recherche actuelle tend à rendre les procédés catalytiques plus propres dans le contexte de la chimie verte. Dans cet esprit, cette thèse a impliqué la recherche de catalyseurs nanoparticulaires utilisés en milieu aqueux, sans ligand toxique et en très faible quantité. La synthèse des nanoparticules (NPs) catalytiques a utilisé des ions des éléments de transition de la droite du tableau périodique et des réducteurs capables de réduire rapidement ces cations en atomes de degré d’oxydation nul s’agrégeant en petites NPs métalliques très actives en catalyse. Les réducteurs choisis ont été des composés réservoirs d’électron organique (naphthyl sodium) ou organométalliques (complexes sandwichs à 19 électrons de valence du fer tel que [Fe(I)Cp*(ŋ6-C6Me6)] ou du cobalt tel que [Co(II)Cp*2], (Cp* = ŋ5-C5Me5)). Les supports limitant l’agrégation des NPs métalliques ont été le solvant (polyéthylène glycol, 1ère partie de la thèse), les cations des réservoirs d’électron organométalliques (2ème partie de la thèse) ou un réseau zéolitique imidazolate (MOF de type ZIF-8, 3ème partie de la thèse). Au lieu d’un cation métallique, il a aussi été possible d’utiliser un cluster tel que [Au25(SR)18] (R = CH2CH2Ph) comme précurseur, auquel cas la réduction peut se limiter à un simple transfer d’électron produisant un cluster anionique stabilisé par le contre-cation sandwich encombré du réservoir d’électron. Les petites NPs ainsi stabilisées se sont avérées d’excellents catalyseurs “verts” de plusieurs réactions de couplage C-C ou C-N et de production d’hydrogène par hydrolyse d’hydrures métalliques en milieu aqueux dans des conditions très douces. Cette dernière réaction a été efficacement catalysée par des NPs bimétalliques Ni2Pt NP@ZIF-8 avec une synergie spectaculaire entre les deux métaux. / Catalysis is a key element in chemical synthesis, and current research is focusing on making catalytic processes cleaner in the context of green chemistry. In this spirit, this thesis involves the research of nanoparticle (NP) catalysts used in aqueous medium, without toxic ligand and in very small quantities toward a variety of useful processes. The synthesis of the catalytic NPs used cations of the transition elements of the right of the periodic table and of reducing agents capable of rapidly reducing these cations to atoms of zero oxidation state aggregating into small catalytically active metal NPs. The chosen reducing agents were organic (naphthyl sodium) or organometallic (19-electron) sandwich complexes of iron such as [Fe(I)Cp*(ŋ6-C6Me6)] or cobalt such as [Co(II)Cp*2], (Cp* = ŋ5-C5Me5)) used as electron reservoirs. The supports limiting the aggregation of the metal NPs were the solvent (polyethylene glycol, first part of the thesis), the cations of the organometallic electron reservoirs (2nd part of the thesis) or a zeolitic imidazolate framework (MOF of ZIF-8 type, 3rd part of the thesis). Instead of a metal cation, it has also been possible to use a cluster such as [Au25(SR) 18] (R = CH2CH2Ph) as a precursor, in which case the reduction was limited to a simple electron transfer producing an anionic cluster stabilized by the congested sandwich counter cation of the electron reservoir. The small NPs thus stabilized proved to be excellent "green" catalysts for several C-C or C-N reactions and hydrogen production by hydrolysis of metal hydrides in an aqueous medium under very mild conditions. This latter reaction was efficiently catalyzed by Ni2Pt@ZIF-8 bimetallic NPs with a spectacular synergy between the two metals.