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1.
Understanding the catalyst compositional and structural features that control selectivity is of uttermost importance to target desired products in chemical reactions. In this joint experimental–computational work, we leverage tailored Cu/ZnO precatalysts as a material platform to identify the intrinsic features of methane-producing and ethanol-producing CuZn catalysts in the electrochemical CO2 reduction reaction (CO2RR). Specifically, we find that Cu@ZnO nanocrystals, where a central Cu domain is decorated with ZnO domains, and ZnO@Cu nanocrystals, where a central ZnO domain is decorated with Cu domains, evolve into Cu@CuZn core@shell catalysts that are selective for methane (∼52%) and ethanol (∼39%), respectively. Operando X-ray absorption spectroscopy and various microscopy methods evidence that a higher degree of surface alloying along with a higher concentration of metallic Zn improve the ethanol selectivity. Density functional theory explains that the combination of electronic and tandem effects accounts for such selectivity. These findings mark a step ahead towards understanding structure–property relationships in bimetallic catalysts for the CO2RR and their rational tuning to increase selectivity towards target products, especially alcohols.

A higher degree of surface alloying and Zn concentration boosts the selectivity towards ethanol of CuZn catalysts in CO2 electroreduction.  相似文献   

2.
Iron-catalyzed organic reactions have been attracting increasing research interest but still have serious limitations on activity, selectivity, functional group tolerance, and stability relative to those of precious metal catalysts. Progress in this area will require two key developments: new ligands that can impart new reactivity to iron catalysts and elucidation of the mechanisms of iron catalysis. Herein, we report the development of novel 2-imino-9-aryl-1,10-phenanthrolinyl iron complexes that catalyze both anti-Markovnikov hydrosilylation of terminal alkenes and 1,2-anti-Markovnikov hydrosilylation of various conjugated dienes. Specifically, we achieved the first examples of highly 1,2-anti-Markovnikov hydrosilylation reactions of aryl-substituted 1,3-dienes and 1,1-dialkyl 1,3-dienes with these newly developed iron catalysts. Mechanistic studies suggest that the reactions may involve an Fe(0)–Fe(ii) catalytic cycle and that the extremely crowded environment around the iron center hinders chelating coordination between the diene and the iron atom, thus driving migration of the hydride from the silane to the less-hindered, terminal end of the conjugated diene and ultimately leading to the observed 1,2-anti-Markovnikov selectivity. Our findings, which have expanded the types of iron catalysts available for hydrosilylation reactions and deepened our understanding of the mechanism of iron catalysis, may inspire the development of new iron catalysts and iron-catalyzed reactions.

Newly developed iron complexes bearing 2-imino-9-aryl-1,10-phenanthroline ligands were successfully used to catalyze hydrosilylation of terminal alkenes and conjugated dienes in high yields with excellent anti-Markovnikov selectivity.  相似文献   

3.
Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.

Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions.  相似文献   

4.
Chiral recognition and discrimination is not only of significance in biological processes but also a powerful method to fabricate functional supramolecular materials. Herein, a pair of heterochiral porous organic cages (HPOC-1), out of four possible enantiomeric products, with mirror stereoisomeric crystal structures were cleanly prepared by condensation occurring in the exclusive combination of cyclohexanediamine and binaphthol-based tetraaldehyde enantiomers. Nuclear magnetic resonance and luminescence spectroscopy have been employed to monitor the assembly process of HPOC-1, revealing the clean formation of heterochiral organic cages due to the enantioselective recognition of (S,S)-binaphthol towards (R,R)-cyclohexanediamine derivatives and vice versa. Interestingly, HPOC-1 exhibits circularly polarized luminescence and enantioselective recognition of chiral substrates according to the circular dichroism spectral change. Theoretical simulations have been carried out, rationalizing both the enantioselective assembly and recognition of HPOC-1.

Heterochiral organic cages based on enantioselective self-assembly of binary chiral components have been prepared, exhibiting circularly polarized luminescence property and enantioselective recognition ability towards chiral substrates according to the circular dichroism spectral change.  相似文献   

5.
PtCu single-atom alloys (SAAs) open an extensive prospect for heterogeneous catalysis. However, as the host of SAAs, Cu suffers from severe sintering at elevated temperature, resulting in poor stability of catalysts. This paper describes the suppression of the agglomeration of Cu nanoparticles under high temperature conditions using copper phyllosilicate (CuSiO3) as the support of PtCu SAAs. Based on quasi in situ XPS, in situ CO-DRIFTS, in situ Raman spectroscopy and in situ XRD, we demonstrated that the interfacial Cu+–O–Si formed upon reduction at 680 °C serves as the adhesive between Cu nanoparticles and the silicon dioxide matrix, strengthening the metal–support interaction. Consequently, the resistance to sintering of PtCu SAAs was improved, leading to high catalytic stability during propane dehydrogenation without sacrificing conversion and selectivity. The optimized PtCu SAA catalyst achieved more than 42% propane conversion and 93% propylene selectivity at 580 °C for at least 30 hours. It paves a way for the design and development of highly active supported single-atom alloy catalysts with excellent thermal stability.

This paper describes PtCu single-atom alloys supported on copper phyllosilicate via Cu+–O–Si. The catalyst exhibits sintering resistance in propane dehydrogenation reaction without sacrificing activity and selectivity.  相似文献   

6.
External control of chemical processes is a subject of widespread interest in chemical research, including control of electrocatalytic processes with significant promise in energy research. The electrochemical double-layer is the nanoscale region next to the electrode/electrolyte interface where chemical reactions typically occur. Understanding the effects of electric fields within the electrochemical double layer requires a combination of synthesis, electrochemistry, spectroscopy, and theory. In particular, vibrational sum frequency generation (VSFG) spectroscopy is a powerful technique to probe the response of molecular catalysts at the electrode interface under bias. Fundamental understanding can be obtained via synthetic tuning of the adsorbed molecular catalysts on the electrode surface and by combining experimental VSFG data with theoretical modelling of the Stark shift response. The resulting insights at the molecular level are particularly valuable for the development of new methodologies to control and characterize catalysts confined to electrode surfaces. This Perspective article is focused on how systematic modifications of molecules anchored to surfaces report information concerning the geometric, energetic, and electronic parameters of catalysts under bias attached to electrode surfaces.

Heterogeneous electrocatalysis: characterization of interfacial electric field within the electrochemical double layer.  相似文献   

7.
Organophosphonate compounds have represented a rich source of biologically active compounds, including enzyme inhibitors, antibiotics, and antimalarial agents. Here, we report the development of a highly stereoselective strategy for olefin cyclopropanation in the presence of a phosphonyl diazo reagent as carbene precursor. In combination with a ‘substrate walking’ protein engineering strategy, two sets of efficient and enantiodivergent myoglobin-based biocatalysts were developed for the synthesis of both (1R,2S) and (1S,2R) enantiomeric forms of the desired cyclopropylphosphonate ester products. This methodology enables the efficient transformation of a broad range of vinylarene substrates at a preparative scale (i.e. gram scale) with up to 99% de and ee. Mechanistic studies provide insights into factors that contribute to make this reaction inherently more challenging than hemoprotein-catalyzed olefin cyclopropanation with ethyl diazoacetate investigated previously. This work expands the range of synthetically useful, enzyme-catalyzed transformations and paves the way to the development of metalloprotein catalysts for abiological carbene transfer reactions involving non-canonical carbene donor reagents.

Two enantiocomplementary myoglobin-based carbene transfer biocatalysts were developed for the synthesis of cyclopropylphosphonate esters with high diastereo- and enantioselectivity and in high yields.  相似文献   

8.
Although research on iron-catalysed reactions has recently achieved significant progress, the activity and selectivity of iron catalysts are generally inferior to those of noble-metal catalysts. The development of new iron-catalysed reactions, especially those in which iron catalysts exhibit superior activity or selectivity to other catalysts, is the key to promote iron catalysis. Herein, we report the first protocol for iron-catalysed hydroalumination of internal alkynes. Specifically, in the presence of iron catalysts bearing 2,9-diaryl-1,10-phenanthroline ligands, internal alkynes were stereo- and regioselectively hydroaluminated with the commercially available reagent diisobutylaluminum hydride. Compared with other metal-catalysed alkyne hydroalumination reactions reported in the literature, the iron-catalysed protocol has the following advantages: unusual amino-group-directed regioselectivity, a wide substrate scope, good functional group tolerance, high selectivity, and mild reaction conditions. The alkenylaluminum products prepared in this way could undergo a diverse array of transformations, and were used for the synthesis of bioactive compounds. The current study expands the scope of iron catalysis, provides a new efficient access to alkenylaluminum, discloses the origin of the superiority of iron catalysts, and thus may inspire further studies in related fields.

An iron-catalysed hydroalumination of internal alkynes featuring with unusual amino-group-directed regioselectivity, a wide substrate scope, good functional group tolerance, high selectivity, and mild reaction conditions was realized.  相似文献   

9.
Carbon dioxide derived polymers are emerging as useful materials for applications spanning packaging, construction, house-hold goods and automotive components. To accelerate and broaden their uptake requires both more active and selective catalysts and greater structural diversity for the carbon dioxide derived polymers. Here, highly active catalysts show controllable selectivity for the enchainment of mixtures of epoxide, anhydride, carbon dioxide and lactone. Firstly, metal dependent selectivity differences are uncovered using a series of dinuclear catalysts, Mg(ii)Mg(ii), Zn(ii)Zn(ii), Mg(ii)Zn(ii), and Mg(ii)Co(ii), each exposed to mixtures of bio-derived tricyclic anhydride, cyclohexene oxide and carbon dioxide (1 bar). Depending upon the metal combinations, different block structures are possible with Zn(ii)Zn(ii) yielding poly(ester-b-carbonate); Mg(ii)Mg(ii) or Mg(ii)Co(ii) catalysts delivering poly(carbonate-b-ester); and Mg(ii)Zn(ii) furnishing a random copolymer. These results indicate that carbon dioxide insertion reactions follow the order Co(ii) > Mg(ii) > Zn(ii). Using the most active and selective catalyst, Mg(ii)Co(ii), and exploiting reversible on/off switches between carbon dioxide/nitrogen at 1 bar delivers precision triblock (ABA), pentablock (BABAB) and heptablock (ABABABA) polymers (where A = poly(cyclohexylene oxide-alt-tricyclic anhydride), PE; B = poly(cyclohexene carbonate), PCHC). The Mg(ii)Co(ii) catalyst also selectively polymerizes a mixture of anhydride, carbon dioxide, cyclohexene oxide and ε-caprolactone to deliver a CBABC pentablock copolymer (A = PE, B = PCHC C = poly(caprolactone), PCL). The catalysts combine high activity and selectivity to deliver new polymers featuring regularly placed carbon dioxide and biomass derived linkages.

Carbon dioxide-based multiblock polymers are synthesised, in one-pot, from a mixture of monomers using a highly selective and active heterodinuclear Co(ii)Mg(ii) catalyst.  相似文献   

10.
This study uses X-ray crystallography, theory and Langmuir isotherm analysis to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes. Favoured conformations retain the more polar triaxial C–F bond arrangement of the all-cis 2,3,4,5,6-pentafluorocyclohexyl ring systems with the alkyl substituent adopting an equatorial orientation, and accommodating strong supramolecular interactions between rings. Langmuir isotherm analysis on a water subphase of a long chain fatty acid and alcohol carrying terminal all-cis 2,3,4,5,6-pentafluorocyclohexyl rings do not show any indication of monolayer assembly relative to their cyclohexane analogues, instead the molecules appear to aggregate and form higher molecular assemblies prior to compression. The study indicates the power and potential of this ring system as a motif for ordering supramolecular assembly.

Theory and Langmuir isotherm analysis was used to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes.  相似文献   

11.
Molecular catalysts show powerful catalytic efficiency and unsurpassed selectivity in many reactions of interest. As their implementation in electrocatalytic devices requires their immobilization onto a conductive support, controlling the grafting chemistry and its impact on their distribution at the surface of this support within the catalytic layer is key to enhancing and stabilizing the current they produce. This study focuses on molecular bioinspired nickel catalysts for hydrogen oxidation, bound to carbon nanotubes, a conductive support with high specific area. We couple advanced analysis by transmission electron microscopy (TEM), for direct imaging of the catalyst layer on individual nanotubes, and small angle neutron scattering (SANS), for indirect observation of structural features in a relevant aqueous medium. Low-dose TEM imaging shows a homogeneous, mobile coverage of catalysts, likely as a monolayer coating the nanotubes, while SANS unveils a regular nanostructure in the catalyst distribution on the surface with agglomerates that could be imaged by TEM upon aging. Together, electrochemistry, TEM and SANS analyses allowed drawing an unprecedented and intriguing picture with molecular catalysts evenly distributed at the nanoscale in two different populations required for optimal catalytic performance.

How do efficient hydrogen-oxidation molecular electrocatalysts connect onto their carbon nanotube conductive support? A coupled neutron scattering SANS and STEM electron microscopy study to observe soft active matter organizing on 3D nanosurfaces.  相似文献   

12.
A catalytic system based on earth-abundant elements that efficiently hydrogenates aryl olefins using visible light as the driving-force and H2O as the sole hydrogen atom source is reported. The catalytic system involves a robust and well-defined aminopyridine cobalt complex and a heteroleptic Cu photoredox catalyst. The system shows the reduction of styrene in aqueous media with a remarkable selectivity (>20 000) versus water reduction (WR). Reactivity and mechanistic studies support the formation of a [Co–H] intermediate, which reacts with the olefin via a hydrogen atom transfer (HAT). Synthetically useful deuterium-labelled compounds can be straightforwardly obtained by replacing H2O with D2O. Moreover, the dual photocatalytic system and the photocatalytic conditions can be rationally designed to tune the selectivity for aryl olefin vs. aryl ketone reduction; not only by changing the structural and electronic properties of the cobalt catalysts, but also by modifying the reduction properties of the photoredox catalyst.

A dual catalytic system based on earth-abundant elements reduces aryl olefins to alkanes in aqueous media under visible light. Mechanistic studies allow for rational tunning of the system for the selective reduction of aryl olefins vs ketones and vice versa.  相似文献   

13.
Selective oxidative cleavage of the C(CO)–C bond in ketones to access esters is a highly attractive strategy for upgrading ketones. However, it remains a great challenge to realize this important transformation over heterogeneous metal-free catalysts. Herein, we designed a series of porous and ultrathin N-doped carbon nanosheets (denoted as CN-X, where X represents the pyrolysis temperature) as heterogeneous metal-free catalysts. It was observed that the fabricated CN-800 could efficiently catalyze the oxidative cleavage of the C(CO)–C bond in various ketones to generate the corresponding methyl esters at 130 °C without using any additional base. Detailed investigations revealed that the higher content and electron density of the graphitic-N species contributed to the excellent performance of CN-800. Besides, the high surface area, affording active sites that are more easily accessed, could also enhance the catalytic activity. Notably, the catalysts have great potential for practical applications because of some obvious advantages, such as low cost, neutral reaction conditions, heterogeneous nature, high efficiency, and broad ketone scope. To the best of our knowledge, this is the first work on efficient synthesis of methyl esters via oxidative esterification of ketones over heterogeneous metal-free catalysts.

Ultrathin and metal-free N-doped carbon nanosheets showed high activity and selectivity for oxidative esterification of ketones via C(CO)–C bond cleavage to access methyl esters.  相似文献   

14.
Two full-length analogs of the anticancer peptide yaku''amide A (1a) and four partial structures have been synthesized. These analogs were identified by computational studies in which the three E- and Z-ΔIle residues of the natural product were replaced by the more accessible dehydroamino acids ΔVal and ΔEnv. Of the eight possible analogs, modeling showed that the targeted structures 2a and 2b most closely resembled the three-dimensional structure of 1a. Synthesis of 2a and 2b followed a convergent route that was streamlined by the absence of ΔIle in the targets. Screening of the compounds against various cancer cell lines revealed that 2a and 2b mimic the potent anticancer activity of 1a, thereby validating the computational studies.

Simplified full-length analogs of yaku''amide A were designed with the aid of computations and then synthesized. The analog that was predicted to most closely resemble the structure of the natural product mimicked its anticancer activity.  相似文献   

15.
16.
Bimetallic catalysts provide opportunities to overcome scaling laws governing selectivity of CO2 reduction (CO2R). Cu/Au nanoparticles show promise for CO2R, but Au surface segregation on particles with sizes ≥7 nm prevent investigation of surface atom ensembles. Here we employ ultrasmall (2 nm) Cu/Au nanoparticles as catalysts for CO2R. The high surface to volume ratio of ultrasmall particles inhibits formation of a Au shell, enabling the study of ensemble effects in Cu/Au nanoparticles with controllable composition and uniform size and shape. Electrokinetics show a nonmonotonic dependence of C1 selectivity between CO and HCOOH, with the 3Au:1Cu composition showing the highest HCOOH selectivity. Density functional theory identifies Cu2/Au(211) ensembles as unique in their ability to synthesize HCOOH by stabilizing CHOO* while preventing H2 evolution, making C1 product selectivity a sensitive function of Cu/Au surface ensemble distribution, consistent with experimental findings. These results yield important insights into C1 branching pathways and demonstrate how ultrasmall nanoparticles can circumvent traditional scaling laws to improve the selectivity of CO2R.

Bimetallic catalysts provide opportunities to overcome scaling laws governing C1 selectivity of CO2 reduction (CO2R).  相似文献   

17.
Formate and CO are competing products in the two-electron CO2 reduction reaction (2e CO2RR), and they are produced via *OCHO and *COOH intermediates, respectively. However, the factors governing CO/formate selectivity remain elusive, especially for metal–carbon–nitrogen (M–N–C) single-atom catalysts (SACs), most of which produce CO as their main product. Herein, we show computationally that the selectivity of M–N–C SACs is intrinsically associated with the CO2 adsorption mode by using bismuth (Bi) nanosheets and the Bi–N–C SAC as model catalysts. According to our results, the Bi–N–C SAC exhibits a strong thermodynamic preference toward *OCHO, but under working potentials, CO2 is preferentially chemisorbed first due to a charge accumulation effect, and subsequent protonation of chemisorbed CO2 to *COOH is kinetically much more favorable than formation of *OCHO. Consequently, the Bi–N–C SAC preferentially produces CO rather than formate. In contrast, the physisorption preference of CO2 on Bi nanosheets contributes to high formate selectivity. Remarkably, this CO2 adsorption-based mechanism also applies to other typical M–N–C SACs. This work not only resolves a long-standing puzzle in M–N–C SACs, but also presents simple, solid criteria (i.e., CO2 adsorption modes) for indicating CO/formate selectivity, which help strategic development of high-performance CO2RR catalysts.

This report discloses a nontrivial role of the CO2 adsorption mode in governing the CO/formate selectivity of single-atom catalysts towards two-electron CO2 reduction.  相似文献   

18.
Copper-based catalysts are efficient for CO2 reduction affording commodity chemicals. However, Cu(i) active species are easily reduced to Cu(0) during the CO2RR, leading to a rapid decay of catalytic performance. Herein, we report a hybrid-catalyst that firmly anchors 2D-Cu metallic dots on F-doped CuxO nanoplates (CuxOF), synthesized by electrochemical-transformation under the same conditions as the targeted CO2RR. The as-prepared Cu/CuxOF hybrid showed unusual catalytic activity towards the CO2RR for CH3COO generation, with a high FE of 27% at extremely low potentials. The combined experimental and theoretical results show that nanoscale hybridization engenders an effective s,p-d coupling in Cu/CuxOF, raising the d-band center of Cu and thus enhancing electroactivity and selectivity for the acetate formation. This work highlights the use of electronic interactions to bias a hybrid catalyst towards a particular pathway, which is critical for tuning the activity and selectivity of copper-based catalysts for the CO2RR.

A two-dimensional (2D) copper hybrid catalyst (Cu/CuxOF) composed of metallic Cu well dispersed on 2D F-doped CuxO nanoplates (CuxOF) is reported, which shows high catalytic activity toward the CO2RR for acetate generation.  相似文献   

19.
Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from identical starting materials. We describe here a solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes with sulfonyl chlorides for the direct construction of highly functionalized cyclopentenones and dihydropyranols that widely exist in bioactive molecules and natural products. Density functional theory calculations suggest that a unique N,N-dimethylacetamide-assisted 1,2-hydrogen transfer of alkoxy radicals is responsible for the cyclopentenone formation, whereas a C–C cleavage accounts for the selective production of dihydropyranols in acetonitrile and water at 50 °C. Given the simple and mild reaction conditions, excellent functional group compatibility, forming up to four chemical bonds, and tunable selectivity, it may find wide applications in synthetic chemistry.

A solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes is developed, providing a facile access to sulfonylated cyclopentenones and dihydropyranols under mild conditions.  相似文献   

20.
Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation. This conversion mainly focuses on transition metal-catalyzed anodic oxidation and cathodic reduction and great progress has been achieved in both areas. Typically, only one of the half-cell reactions is involved in the organic reaction while a sacrificial reaction occurs at the counter electrode, which is inherently wasteful since one electrode is not being used productively. Recently, transition metal-catalyzed paired electrolysis that makes use of both anodic oxidation and cathodic reduction has attracted much attention. This perspective highlights the recent progress of each type of electrochemical reaction and relatively focuses on the transition metal-catalyzed paired electrolysis, showcasing that electrochemical reactions involving transition metal catalysis have advantages over conventional reactions in terms of controlling the reaction activity and selectivity and figuring out that transition metal-catalyzed paired electrolysis is an important direction of organic electrochemistry in the future and offers numerous opportunities for new and improved organic reaction methods.

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation.  相似文献   

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