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Colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) perovskite nanocrystals (NCs) hold promises in photovoltaic and optoelectronic applications. However, their poor long‐term stability results in degradation of optical properties under ambient conditions. Various methods have been explored to address these issues. In this study, we demonstrate that following 3‐precursor hot‐injection method employing ethylenediammonium dihalide (EDAX2) as an additional ligand/halide source one can obtain phase‐pure, monodispersed, stable, and highly luminescent CsPbX3 NCs. Our violet‐emitting CsPbCl3, blue‐emitting CsPbClBr2, Green‐emitting CsPbBr3, yellow‐emitting CsPbBr2I, and red‐emitting CsPbI3 NCs show PLQYs of 53%, 97%, 96%, 93%, and 95%, respectively. Moreover, the CsPbI3 NCs, which are known for their phase instability, exhibit stability for up to two months under ambient conditions. The enhanced stability and photoluminescence are attributed to strong binding of the bidentate ligand (EDA2+) to the surface of the NCs and effective removal of the halide‐deficiency trap states by X−. [ABSTRACT FROM AUTHOR]

Summary: The synthesis of octenyl succinic anhydride‐modified starch was achieved through a fluidised bed activated by jet milling with graded revolution rates of 1200, 1800, 2400, 3000, and 3600 rpm. This study investigated the changes in the structural, physicochemical, and application properties of modified starch after jet milling. The results showed that modified starch can be synthesised using a one‐step jet milling process. The degree of substitution increased with a decrease in the starch particle size, resulting in a rough granule morphology. Structural analysis revealed that crystalline areas were destroyed in the modified starches. In the Fourier‐infrared spectrum, typical peaks appeared at 1724 and 1573 cm−1 upon introduction of the octenyl succinic anhydride group, whereas a new sodium peak appeared in the XPS spectrogram. The 1H‐NMR spectrum indicated that the esterification reaction mainly occurred on OH2 groups. The emulsification properties of the modified starch were significantly enhanced and increased with the crushing strength. The octenyl succinic anhydride‐modified starch has potential as a wall material for microcapsules, with good embedding rate and thermal stability. This novel synthesis method represents an innovative method for the synthesis of OSA‐starches. [ABSTRACT FROM AUTHOR]

Compounds containing a 2‐deoxy β‐glycoside linkage play important roles in carbohydrate chemistry, serving as potential therapies with significant biological properties. From the viewpoint of synthesis, many strategies developed in recent years targeted the stereoselective construction of 2‐deoxy glycosides. This review aims to summarise recent advances in the synthetic routes toward 2‐deoxy β‐glycosides developed over the last decade. Where associated, practical applications of these strategies in the total synthesis of natural products are highlighted. [ABSTRACT FROM AUTHOR]

The intrinsic lack of processability in the conventional nano/microcrystalline powder form of metal‐organic frameworks (MOFs) greatly limits their application in various fields. Synthesis of MOFs with certain flowability make them promising for multitudinous applications. The direct synthesis strategy represents one of the simplest and efficient method for synthesizing solution processable MOF sols/suspensions, compared with other approaches, for instance, the post‐synthesis surface modification, the direct dispersion of MOFs in hindered ionic liquids, as well as the calcination method toward a few MOFs with melting behavior. This article reviews the recent direct synthesis strategies of solution processable MOF sols and their typical applications in different fields. The direct synthesis strategies of MOF sols can be classified into two categories: particle size reduction strategy, and selective coordination strategy. The synthesis mechanism of different strategies and the factors affecting the formation of sols are summarized. The application of solution processable MOF sols in different fields are introduced, showing great application potentials. Furthermore, the challenges faced by the direct synthesis of MOF sols and the main methods to deal with the challenges are emphasized, and the future development trend is prospected. [ABSTRACT FROM AUTHOR]

Phase engineering of CsPbI3 nanocrystals (NCs) is a priority for their optoelectronic applications. So far, the scalable and room‐temperature direct synthesis of black phase CsPbI3 NCs remains an enormous challenge because of the thermal unequilibrium‐induced phase transition. Herein the direct synthesis is reported of metastable β‐CsPbI3 NCs in gram‐scale at room‐temperature in seconds via spontaneous crystallization. The obtained β‐CsPbI3 NCs exhibit good monodispersity, narrow‐band far‐red emission (716 nm, FWHM = 38 nm) as well as a high photoluminescence quantum yield of 62%. The crystallization dynamics of β‐CsPbI3 NCs are revealed through in situ UV–vis absorption and photoluminescence spectra analysis. Finally, a photon‐to‐photon conversion indirect X‐ray detector based on the phase‐stable NCs/polystyrene film is preliminarily demonstrated. This scalable and low‐cost preparation of high‐quality metastable β‐CsPbI3 NCs will pave the way for their future commercial applications in novel optoelectronic devices. [ABSTRACT FROM AUTHOR]

The interaction of 1‐phenyl‐1,4‐dihydro‐5H‐tetrazol‐5‐one (Hpto) with ethylenediamine (en) and metallic copper in ethanol in the open air was found to yield molecular complexes [Cu(en)2(pto)2] (1) or [Cu2(en)2(EtOH)2(pto)4] (2) depending on the reagents ratio. Deprotonated tetrazol‐5‐one, i.e 1‐phenyltetrazol‐5‐olate anion (pto) acts as a monodentate ligand coordinated to the metal via the tetrazole ring N4 atom in mononuclear complex 1, and as a bridging ligand coordinated via the tetrazole ring N4 and N3 atoms in binuclear complex 2. The latter was found to be a paramagnet, with a very weak antiferromagnetic exchange interaction between copper ions. [ABSTRACT FROM AUTHOR]

The direct synthesis of hydrogen peroxide has been for about 20 years a hot topic in "green" catalysis. Several methods, which are well established to measure the concentration of hydrogen peroxide in water are also applied to the analysis of reaction mixtures from the direct synthesis of H2O2. However, this step could not be always straightforward, because these mixtures contain almost invariably organic solvents and, sometimes, selectivity enhancers which can interfere in some, at the least, of the most popular titrimetric methods. This work presents a comparative investigation of iodometry, cerimetry, permanganometry (titrimetric methods) and spectrophotometric analysis of TiIV/H2O2 adduct, as applied to analysis of hydrogen peroxide produced by its direct synthesis. They account for more than 90 % of the competent literature since 2000. Their pros and cons are highlighted to provide a guideline for the choice of the best possible method of analysis and for the comparison of catalytic results assessed in different ways in the context of the direct synthesis of hydrogen peroxide. [ABSTRACT FROM AUTHOR]

Spin‐crossover complexes form one of the biggest families of switchable compounds. Here we show a new way to obtain spin‐crossover materials by direct synthesis from metallic iron. Four complexes of FeII with 4‐R‐1,2,4‐triazoles have been synthesized by a direct metal oxidation: [Fe(NH2trz)3]SO4, [Fe(NH2trz)3](BF4)2 and two polymorphs of [Fe(Htrz)2(trz)]BF4. Surprisingly high quality of PXRD pattern of [Fe(NH2trz)3]SO4 allowed to perform Rietveld refinement and obtain reliable crystal structure of the latter. All compounds have been studied by magnetic susceptibility measurements, optical reflectivity, differential scanning calorimetry and Raman spectroscopy. Importantly, spin‐crossover characteristics of the complexes obtained by this unusual method are preserved, thus revealing a new effective approach of "direct synthesis" towards switchable coordination compounds. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have aroused worldwide interest over the last two decades due to their various excellent properties, such as porosity, modifiability, stability, etc. Based on these unique features, they have been widely exploited for applications from electrocatalysis to electrochemical devices. However, most MOFs are inherently insulated due to the lack of free charge carriers and low‐energy barriers for charge transfer, which largely restricts their further electrochemical applications. By imparting MOFs with electrical conductivity, their electrochemical process and catalysis efficiency can be effectively improved. Similarly, their applications in sensors, secondary batteries, electrochemical devices, etc., can be well developed. Over the past few years, many conductive MOFs have been constructed by formatting composite, postsynthesized modification, introducing guest molecules, etc. Meanwhile, their electrochemical applications depending on their good conductivity have been investigated detailedly. However, it remains a challenge to endow most MOFs with high conductivity due to the tedious synthesis process and weak charge transfer properties of MOFs. In this review, the latest designs and synthesis strategies of conductive MOFs as well as their conductive mechanisms are summarized. The direct/postsynthesis methods are mainly focused for constructing conductive MOFs. In addition, their applications in sensors, energy conversion, electronics, etc., are also introduced. [ABSTRACT FROM AUTHOR]

There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet‐like crystal morphology, large surface area, fully four‐coordinated Al species, and abundant acidic sites. Methanol‐to‐propylene (MTP) tests reveal that the Al‐ITH zeolite shows much higher selectivity for propylene and longer lifetime than commercial ZSM‐5. FCC tests show that Al‐ITH zeolite is a good candidate as a shape‐selective FCC additive for enhancing propylene and butylene selectivity. [ABSTRACT FROM AUTHOR]

In this article, we report a one‐pot synthesis strategy to directly synthesize the hierarchical FeCu‐ZSM‐5 zeolite. Its physicochemical properties were studied by various characterization techniques and catalytic performance was tested in selective catalytic reduction (SCR) of NO with NH3 as reductant. The characterization results show that: compared with three reference zeolites Fe/ZSM‐5, Cu/ZSM‐5, and Fe/Cu/ZSM‐5 prepared through an incipient wetness impregnation method, the synthesized FeCu‐ZSM‐5 zeolite exhibits hierarchical micro‐mesoporous structures, more Fe3+ in zeolite framework, and larger isolated Cu2+ species. Therefore, when used as a catalyst in NH3‐SCR, the resulting hierarchical FeCu‐ZSM‐5 catalyst shows better catalytic performance (high NO conversion and N2 selectivity) in a wide temperature window and higher hydrothermal stability than the three reference catalysts. Our work provides a simple and facile route to prepare the promising NH3‐SCR catalyst for practical applications in controlling NOx emissions. [ABSTRACT FROM AUTHOR]

In this article, we report a one‐pot synthesis strategy to directly synthesize the hierarchical FeCu‐ZSM‐5 zeolite. Its physicochemical properties were studied by various characterization techniques and catalytic performance was tested in selective catalytic reduction (SCR) of NO with NH3 as reductant. The characterization results show that: compared with three reference zeolites Fe/ZSM‐5, Cu/ZSM‐5, and Fe/Cu/ZSM‐5 prepared through an incipient wetness impregnation method, the synthesized FeCu‐ZSM‐5 zeolite exhibits hierarchical micro‐mesoporous structures, more Fe3+ in zeolite framework, and larger isolated Cu2+ species. Therefore, when used as a catalyst in NH3‐SCR, the resulting hierarchical FeCu‐ZSM‐5 catalyst shows better catalytic performance (high NO conversion and N2 selectivity) in a wide temperature window and higher hydrothermal stability than the three reference catalysts. Our work provides a simple and facile route to prepare the promising NH3‐SCR catalyst for practical applications in controlling NOx emissions. [ABSTRACT FROM AUTHOR]

The Rochow-Müller process, an old process that has been known for more than seventy years, is for the direct synthesis of methylchlorosilane. However, due to its unique economic efficiency, it is still extremely important in silicone industry, e. g., about 90% of starting materials for producing silicones are obtained by this route. Although significant progress has been made in exploring high-efficient catalysts and understanding its mechanism, a quantitative description of this reaction is still farfetched due to its high complexity. In addition, sustainable use and recycling of by-products and waste solid have become imperative nowadays due to the increasing demands for atom economy and environmental protection. This paper provides a comprehensive overview and insights into Rochow-Müller process from its catalysis to sustainable issues, including the catalyst development and reaction mechanism investigation, waste reutilization and their derived products. In addition, several emerging novel processes originated from Rochow-Müller process are summarized. Lastly, challenges and perspectives with respect to this reaction are discussed. We hope this work has accurately reflected and recorded the transition of Rochow-Müller process to modern molecular catalysis, and can promote a much more sustainable silicone industry. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H2O2) is a highly effective, green oxidant that has found application in sectors ranging from the synthesis of fine chemicals and waste stream treatment to the extraction of precious metals and the bleaching of paper pulp and textiles. The growing demand for H2O2 has seen it become one of the 100 most important chemicals in the world. The direct synthesis of H2O2 from H2 and O2 has been a challenge for the scientific community for over 100 years and represents an attractive alternative to the current means of production. Herein we discuss the historical perspective of the direct synthesis process, the recent literature regarding catalyst design and the role of additives as well as the application of H2O2 as an in situ oxidant. We discuss the key problems that remain and conclude that although there has been progress with respect to the selectivity of hydrogen utilisation, there is a need to now concentrate on catalyst activity as the key remaining problem requiring a solution is the concentration of H2O2 that can be achieved, especially in flow reactors. No detour! The direct synthesis of hydrogen peroxide represents an atom efficient way to make this important commodity chemical. In this mini review we discuss some of the latest advances for this reaction and also point out the challenge that remain to be solved so that this reaction can be considered ready for commercial exploitation; namely the need for increased catalyst activity so that more concentrated solutions can be synthesised. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H2O2) is a highly effective, green oxidant that has found application in sectors ranging from the synthesis of fine chemicals and waste stream treatment to the extraction of precious metals and the bleaching of paper pulp and textiles. The growing demand for H2O2 has seen it become one of the 100 most important chemicals in the world. The direct synthesis of H2O2 from H2 and O2 has been a challenge for the scientific community for over 100 years and represents an attractive alternative to the current means of production. Herein we discuss the historical perspective of the direct synthesis process, the recent literature regarding catalyst design and the role of additives as well as the application of H2O2 as an in situ oxidant. We discuss the key problems that remain and conclude that although there has been progress with respect to the selectivity of hydrogen utilisation, there is a need to now concentrate on catalyst activity as the key remaining problem requiring a solution is the concentration of H2O2 that can be achieved, especially in flow reactors. No detour! The direct synthesis of hydrogen peroxide represents an atom efficient way to make this important commodity chemical. In this mini review we discuss some of the latest advances for this reaction and also point out the challenge that remain to be solved so that this reaction can be considered ready for commercial exploitation; namely the need for increased catalyst activity so that more concentrated solutions can be synthesised. [ABSTRACT FROM AUTHOR]

The direct synthesis of organocalcium compounds (heavy Grignard reagents) by the reduction of organyl halides with activated calcium powder succeeded in a straightforward manner for organic bromides and iodides that are bound at sp2‐hybridized carbon atoms. Extension of this strategy to alkyl halides was very limited, and only the reduction of trialkylsilylmethyl bromides and iodides with activated calcium allowed the isolation of the corresponding heavy Grignard reagents. Substitution of only one hydrogen atom of the methylene moiety by a phenyl or methyl group directed this reduction toward the Wurtz‐type coupling and the formation of calcium halide and the corresponding C−C coupling product. The stability of the methylcalcium and benzylcalcium derivatives in ethereal solvents suggests an unexpected reaction behavior of the intermediate organyl halide radical anions. Quantum chemical calculations verify a dependency between the ease of preparative access to organocalcium complexes and the C−I bond lengths of the organyl iodides. The bulkiness of the trialkylsilyl group is of minor importance. Chloromethyltrimethylsilane did not react with activated calcium; however, halogen‐exchange reactions allowed the isolation of [Ca(CH2SiMe3)(thf)3(μ‐Cl)]2. Furthermore, the metathetical approach of reacting [Ca(CH2SiMe3)I(thf)4] with KN(SiMe3)2 and the addition of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdeta) allowed the isolation of heteroleptic [CaCH2SiMe3{N(SiMe3)2}(pmdeta)]. In the reaction of this derivative with phenylsilane, the trimethylsilylmethyl group proved to be more reactive than the bis(trimethylsilyl)amido substituent. Organocalcium complexes: The success of the direct synthesis of heavy Grignard reagents, that is, organocalcium iodides, strongly depends on the C−I bond length of the organyl iodide radical anion that forms after the initial single electron transfer (SET) reaction, yielding either R‐Ca‐I and/or Wurtz‐type C−C coupling products (see scheme). [ABSTRACT FROM AUTHOR]

The Grignard reaction offers a straight forward atom-economic synthesis of organomagnesium halides, which undergo redistribution reactions (Schlenk equilibrium) yielding diorganylmagnesium and magnesium dihalides. The homologous organocalcium complexes (heavy Grignard reagents) gained interest only quite recently owing to several reasons. The discrepancy between the inertness of this heavy alkaline earth metal and the enormous reactivity of its organometallics hampered a vast and timely development after the first investigation more than 100 years ago. In this overview the synthesis of organocalcium reagents is described as is the durability in ethereal solvents. Aryl-, alkenyl-, and alkylcalcium halides are prepared by direct synthesis. Characteristic structural features and NMR parameters are discussed. Ligand redistribution reactions can be performed by addition of potassium tert-butanolate to ethereal solutions of arylcalcium iodides yielding soluble diarylcalcium, whereas sparingly soluble potassium iodide and calcium bis( tert-butanolate) precipitate. Furthermore, reactivity studies with respect to metalation and addition to unsaturated organic compounds and metal-based Lewis acids, leading to the formation of heterobimetallic complexes, are presented. [ABSTRACT FROM AUTHOR]

The present study suggests a new scheme to design a decentralized PI controller for two-input two-output (TITO) processes. The decentralized controller is obtained from the direct synthesis method. The decoupler is derived from a modified decoupler and minimizes the interaction between the loops. Then a new reduced method based on equivalent transfer function (ETF) with relative gain array concept and relative normalized relative gain array concept reduces the decoupled process transfer functions to first-order plus time delay (FOPTD) forms. Further, two PI controllers are obtained in the proposed delay-compensated configuration in terms of the only parameter in every individual loop for the FOPTD transfer functions. Three illustrative examples demonstrate that the performance is verified on the original interactive system and show the effectiveness of the proposed design method. The results confirm the superior performance of the proposed compensation configuration in nominal and robust cases. The proposed method also offers several important advantages compared to other previous methods. [ABSTRACT FROM AUTHOR]

BACKGROUND The catalytic direct synthesis of hydrogen peroxide is a highly interesting alternative process to avoid the current anthraquinone route because it implies significant sustainability improvements. Among all the peroxide applications, its use as an electronic chemical requires very low metallic content. The employment of direct synthesis peroxide as raw material for the ultrapurification process has not been investigated before, so its viability is still pending evaluation. RESULTS Although the improvements of catalyst or reactor performance of the direct synthesis process were not defined as objectives of the work, a maximum peroxide concentration of 2.3% was obtained, which is a very good result considering the low pressure used. Some relationships between the measured metallic concentrations in the obtained chemical and the operating conditions have been very useful to identify the most important conditions (selection of appropriate quality chemicals and proper materials for the installation) to promote the production of hydrogen peroxide with low metallic content. The technical competitiveness of this alternative ultrapurification process was clearly demonstrated as the number of required membrane stages (from 1 to 6 depending on the product quality) is lower than that required by the traditional case. Besides, the process can be considered economically viable if the direct synthesis peroxide can be produced with a total cost below 36.5 $ m−3. CONCLUSION Further investigation, specifically focused on holistic approaches, is still necessary in order to assess the total costs of hydrogen peroxide production by direct synthesis. This way, the current available information could be complemented and the competitiveness of this direct route to obtain hydrogen peroxide for electronic grade chemical production could be more clearly defined. © 2015 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

In the SiO2-Al2O3-TPAOH-NH4OH system through a two-step procedure, the effects of synthesis parameters on the yields and properties of HZSM-5 were studied. As the feeding n(SiO2)/n(Al2O3) ratio increased, the yields of synthesized samples were between 11% and 14% while the crystallinity tended to decrease at the ratio > 300. At the ratio of 150, the yield was 13.7% and the ratio of actual yield to theoretical yield was 93%. The sample shaped ellipse-like particles of 3 × 10−6 m. At the n(NH3)/n(SiO2) ratio of 1.5, the yield was 13.1% and the sample showed regular ellipse-like particles of 2 × 10−6 m. Too high dosage of NH4OH lowered the yield and the crystallinity. The addition of seed crystal favored the HZSM-5 synthesis in high crystallinity. At the addition amount of 4%, the yield reached 13.9% and the sample shaped in spherical particles of 0.5 × 10−6 m. Synthesized HZSM-5 with a surface area of 455 m2·g−1 and intrinsic acidity showed highly catalytic activity toward the methanol conversion to olefins reaction. [ABSTRACT FROM AUTHOR]

A facile synthetic method to prepare thiazolium-based ionic liquids in high yield was developed. The direct alkylation of thiazole was performed using a trialkyl orthoester as both the alkyl donor and the solvent. The synthesized thiazolium salts were subsequently screened for their ability to catalyze the benzoin condensation reaction. Of the salts that were tested, 3-butyl,4,5-dimethyl thiazolium salt, was found to be the best catalyst. [ABSTRACT FROM AUTHOR]

This article draws its motivation from classical model-based controller design methods, such as Direct Synthesis (DS) and Internal Model Control (IMC) methods, and develops a model-based PI-like control scheme for stable systems. The proposed control scheme has been realized in a reset configuration. Furthermore, the control scheme has a tuning parameter, and its control action resembles a PI-like controller. The proposed scheme shows improved performance as compared to that of IMC, Skogestad-IMC-PI, and Skogestad-IMC-PID control schemes. In addition, an automated approach to designing this scheme is proposed. The efficacy of the proposed control scheme is demonstrated via experimental evaluation on a computer-interfaced pilot-scale two-tank system. [ABSTRACT FROM AUTHOR]

A general procedure was developed for the synthesis of diarylcalcium complexes by addition of KO tBu to arylcalcium iodides in THF. Intermediate arylcalcium tert-butanolate dismutates immediately leading to insoluble tert-butanolate precipitates of calcium. Depending on the steric demand and denticity of additional neutral aliphatic azabases, mononuclear or dinuclear complexes trans-[Ca(α -Naph)2(thf)4] ( 1), [Ca(β-Naph)2(thf)4] ( 2), [Ca(Tol)2(tmeda)]2 ( 3), [Ca(Ph)2(tmeda)]2 ( 4), [Ca(Ph)2(pmdta)(thf)] ( 5), [Ca(hmteta)(Ph)2] ( 6), and [Ca([18]C-6)(Ph)2] ( 7) were isolated (Naph=naphthyl; meda= N,N,N′,N′-tetramethylethylenediamine; pmdta= N,N,N′,N′′,N′′-pentamethyldiethylenetriamine; hmteta= N,N,N′,N′′,N′′′,N′′′-hexamethyltriethylenetetramine). The CaC bond lengths vary between 250.8 and 263.5 pm, the ipso-carbon atoms show low-field-shifted resonances in the 13C NMR spectra. [ABSTRACT FROM AUTHOR]

To enhance the scope of heavy calcium-based Grignard reagents, 1,2-dihydro-4-iodonaphthalene ( 1) was reduced with calcium in THF giving tetrakis(thf) (1,2-dihydronaphth-4-yl)calcium iodide ( 2). This derivative represents a 1-alkenylcalcium complex based on X-ray structure determination and NMR data. The stability of this compound is significantly reduced compared with the aromatic naphthylcalcium iodide. [ABSTRACT FROM AUTHOR]

The entry to a reliable and straight‐forward organocalcium chemistry encounters diverse challenges and contradictory findings, blocking a timely and vast development of routine protocols. Ether degradation and Wurtz‐type coupling reactions hinder reproducibility and high yield routes to heavy Grignard reagents. After the investigations of quite robust calcocenes the co‐condensation of calcium and alkyl halide led to the first structurally authenticated dialkylcalcium, initiating a fruitful development of calcium‐based organometallics, leading to a reliable protocol to arylcalcium halides and beyond. Dimethylcalcium and calcium(I) organometallics represent future endeavors. More information can be found in the Review by M. Westerhausen et al. on page 1456 ff. [ABSTRACT FROM AUTHOR]

Grignard Reagent Even though organocalcium chemistry is very young it is evident that a broad field of applications can be expected. Recent experiments demonstrate that these highly reactive heavy Grignard reagents represent valuable tools for metalation of compounds with acidic hydrogen atoms. Furthermore, addition of organocalcium complexes to organic and organometallic substrates allows derivatization reactions. For more details see the Review article by M. Westerhausen et al. on page 1456 ff. [ABSTRACT FROM AUTHOR]

Pd-supported metal-organic framework ( MOF) catalysts have been applied for the direct synthesis of H2O2 from H2 and O2 under intrinsically safe and noncorrosive reaction conditions. The catalytic performance was strongly governed by the properties of the support materials, and the Brønsted acid sites newly introduced on the organic linkers of MOF were proven to be more effective than the Lewis acid sites on the open metal sites in enhancing the H2O2 formation and suppressing its decomposition. Pd/ MIL-101- SO3H was highly efficient in promoting the reaction owing to the contribution from the strong acidity and highly porous nature of the robust MOF support used. The hydrogen peroxide productivity of Pd/ MIL-101- SO3H catalyst reached 361 mmol H2O2 mmol/Pd/h, which was 2.3 or 1.7 times higher than that of the conventional Pd/ HBEA ( SAR = 25) or Pd/sulfonated resin catalyst, respectively. This result clearly demonstrates the promising potential of MOF as a solid acid support material. [ABSTRACT FROM AUTHOR]