Confinement-Induced Biocatalytic Activity Enhancement of Light- and Thermoresponsive Polymer@Enzyme@MOF Composites.

Metal-organic frameworks (MOFs) are favorable hosting materials for fixing enzymes to construct enzyme@MOF composites and to expand the applications of biocatalysts. However, the rigid structure of MOFs without tunable hollow voids and a confinement effect often limits their catalytic activities. Taking advantage of the smart soft polymers to overcome the limitation, herein, a protection protocol to encapsulate the enzyme in zeolitic imidazolate framework-8 (ZIF-8) was developed using a glutathione-sensitive liposome (L) as a soft template. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were first anchored on a light- and thermoresponsive porous poly(styrene-maleic anhydride-N,N-dimethylaminoethyl methacrylate-spiropyran) membrane (PSMDSP) to produce PSMDSP@GOx-HRP, which could provide a confinement effect by switching the UV irradiation or varying the temperature. Afterward, embedding PSMDSP@GOx-HRP in L and encapsulating PSMDSP@GOx-HRP@L into hollow ZIF-8 (HZIF-8) to form PSMDSP@GOx-HRP@HZIF-8 composites were performed, which proceeded during the crystallization of the framework following the removal of L by adding glutathione. Impressively, the biocatalytic activity of the composites was 4.45-fold higher than that of the free enzyme under UV irradiation at 47 °C, which could benefit from the confinement effect of PSMDSP and the conformational freedom of the enzyme in HZIF-8. The proposed composites contributed to the protection of the enzyme against harsh conditions and exhibited superior stability. Furthermore, a colorimetric assay based on the composites for the detection of serum glucose was established with a linearity range of 0.05-5.0 mM, and the calculated LOD value was 0.001 mM in a cascade reaction system. This work provides a universal design idea and a versatile technique to immobilize enzymes on soft polymer membranes that can be encapsulated in porous rigid MOF-hosts. It also holds potential for the development of smart polymer@enzyme@HMOFs biocatalysts with a tunable confinement effect and high catalytic performance.

Metal-Sulfur Interfaces as the Primary Active Sites for Catalytic Hydrogenations.

The determination of catalytically active sites is crucial for understanding the catalytic mechanism and providing guidelines for the design of more efficient catalysts. However, the complex structure of supported metal nanocatalysts (e.g., support, metal surface, and metal-support interface) still presents a big challenge. In particular, many studies have demonstrated that metal-support interfaces could also act as the primary active sites in catalytic reactions, which is well elucidated in oxide-supported metal nanocatalysts but is rarely reported in carbon-supported metal nanocatalysts. Here, we fill the above gap and demonstrate that metal-sulfur interfaces in sulfur-doped carbon-supported metal nanocatalysts are the primary active sites for several catalytic hydrogenation reactions. A series of metal nanocatalysts with similar sizes but different amounts of metal-sulfur interfaces were first constructed and characterized. Taking Ir for quinoline hydrogenation as an example, it was found that their catalytic activities were proportional to the amount of the Ir-S interface. Further experiments and density functional theory (DFT) calculations suggested that the adsorption and activation of quinoline occurred on the Ir atoms at the Ir-S interface. Similar phenomena were found in p-chloronitrobenzene hydrogenation over the Pt-S interface and benzoic acid hydrogenation over the Ru-S interface. All of these findings verify the predominant activity of metal-sulfur interfaces for catalytic hydrogenation reactions and contribute to the comprehensive understanding of metal-support interfaces in supported nanocatalysts.

Sabatier Phenomenon in Hydrogenation Reactions Induced by Single-Atom Density.

The Sabatier principle is a fundamental concept in heterogeneous catalysis that provides guidance for designing optimal catalysts with the highest activities. For the first time, we here report a new Sabatier phenomenon in hydrogenation reactions induced by single-atom density at the atomic scale. We produce a series of Ir single-atom catalysts (SACs) with a predominantly Ir1-P4 coordination structure with densities ranging from 0.1 to 1.7 atoms/nm2 through a P-coordination strategy. When used as the catalysts for hydrogenation, a volcano-type relationship between Ir single-atom density and hydrogenation activity emerges, with a summit at a moderate density of 0.7 atoms/nm2. Mechanistic studies show that the balance between adsorption and desorption strength of the activated H* on Ir single atoms is found to be a key factor for the Sabatier phenomenon. The transferred Bader charge on these Ir SACs is proposed as a descriptor to interpret the structure-activity relationship. In addition, the maximum activity and selectivity can be simultaneously achieved in chemoselective hydrogenation reactions with the optimized catalyst due to the uniform geometric and electronic structures of single sites in SACs. The present study reveals the Sabatier principle as an insightful guidance for the rational design of more efficient and practicable SACs for hydrogenation reactions.

Regulating the electronic structure through charge redistribution in dense single-atom catalysts for enhanced alkene epoxidation.

Inter-site interaction in densely populated single-atom catalysts has been demonstrated to have a crucial role in regulating the electronic structure of metal atoms, and consequently their catalytic performances. We herein report a general and facile strategy for the synthesis of several densely populated single-atom catalysts. Taking cobalt as an example, we further produce a series of Co single-atom catalysts with varying loadings to investigate the influence of density on regulating the electronic structure and catalytic performance in alkene epoxidation with O2. Interestingly, the turnover frequency and mass-specific activity are significantly enhanced by 10 times and 30 times with increasing Co loading from 5.4 wt% to 21.2 wt% in trans-stilbene epoxidation, respectively. Further theoretical studies reveal that the electronic structure of densely populated Co atoms is altered through charge redistribution, resulting in less Bader charger and higher d-band center, which are demonstrated to be more beneficial for the activation of O2 and trans-stilbene. The present study demonstrates a new finding about the site interaction in densely populated single-atom catalysts, shedding insight on how density affects the electronic structure and catalytic performance for alkene epoxidation.

Electronic Oxide-Support Strong Interactions in the Graphdiyne-Supported Cuprous Oxide Nanocluster Catalyst.

The interfacial interaction in supported catalysts is of great significance for heterogeneous catalysis because it can induce charge transfer, regulate electronic structure of active sites, influence reactant adsorption behavior, and eventually affect the catalytic performance. It has been theoretically and experimentally elucidated well in metal/oxide catalysts and oxide/metal inverse catalysts, but is rarely reported in carbon-supported catalysts due to the inertness of traditional carbon materials. Using an example of a graphdiyne-supported cuprous oxide nanocluster catalyst (Cu2O NCs/GDY), we herein demonstrate the strong electronic interaction between them and put forward a new type of electronic oxide-graphdiyne strong interaction, analogous to the concept of electronic oxide/metal strong interactions in oxide/metal inverse catalysts. Such electronic oxide-graphdiyne strong interaction can not only stabilize Cu2O NCs in a low-oxidation state without aggregation and oxidation under ambient conditions but also change their electronic structure, resulting in the optimized adsorption energy for reactants/intermediates and thus leading to improved catalytic activity in the Cu(I)-catalyzed azide-alkyne cycloaddition reaction. Our study will contribute to the comprehensive understanding of interfacial interactions in supported catalysts.

Boosting Chemoselective Hydrogenation of Nitroaromatic via Synergy of Hydrogen Spillover and Preferential Adsorption on Magnetically Recoverable Pt@Fe2 O3.

It is highly desired but challenging to design high performance catalyst for selective hydrogenation of nitro compounds into amino compounds. Herein, a boosting chemoselective hydrogenation strategy on Pt@Fe2 O3 is proposed with gradient oxygen vacancy by synergy of hydrogen spillover and preferential adsorption. Experimental and theoretical investigations reveal that the nitro is preferentially adsorbed onto oxygen vacancy of Pt@Fe2 O3 , meanwhile, the H2 dissociated on Pt nanoparticles and then spillover to approach the nitro for selective hydrogenation (>99% conversion of 4-nitrostyrene, > 99% selectivity of 4-aminostyrene, TOF of 2351 h-1 ). Moreover, the iron oxide support endows the catalyst magnetic retrievability. This high activity, selectivity, and easy recovery strategy provide a promising avenue for selective hydrogenation catalysis of various nitroaromatic.

Uniform single atomic Cu1-C4 sites anchored in graphdiyne for hydroxylation of benzene to phenol.

For single-atom catalysts (SACs), the catalyst supports are not only anchors for single atoms, but also modulators for geometric and electronic structures, which determine their catalytic performance. Selecting an appropriate support to prepare SACs with uniform coordination environments is critical for achieving optimal performance and clarifying the relationship between the structure and the property of SACs. Approaching such a goal is still a significant challenge. Taking advantage of the strong d-π interaction between Cu atoms and diacetylenic in a graphdiyne (GDY) support, we present an efficient and simple strategy for fabricating Cu single atoms anchored on GDY (Cu1/GDY) with uniform Cu1-C4 single sites under mild conditions. The Cu atomic structure was confirmed by combining synchrotron radiation X-ray absorption spectroscopy, X-ray photoelectron spectroscopy and density functional theory (DFT) calculations. The as-prepared Cu1/GDY exhibits much higher activity than state-of-the-art SACs in direct benzene oxidation to phenol with H2O2 reaction, with turnover frequency values of 251 h-1 at room temperature and 1889 h-1 at 60°C, respectively. Furthermore, even with a high benzene conversion of 86%, high phenol selectivity (96%) is maintained, which can be ascribed to the hydrophobic and oleophyllic surface nature of Cu1/GDY for benzene adsorption and phenol desorption. Both experiments and DFT calculations indicate that Cu1-C4 single sites are more effective at activating H2O2 to form Cu=O bonds, which are important active intermediates for benzene oxidation to phenol.

Graphdiyne Nanospheres as a Wettability and Electron Modifier for Enhanced Hydrogenation Catalysis.

Owing to unique alkyne-rich structure, graphdiyne (GDY) has been proven to be a superb support for anchoring metal catalysts. Herein we demonstrate a new role of GDY as the wettability modifier for enhanced hydrogenation catalysis. After loading a certain amount GDY nanospheres, the silica mesoporous channels become superaerophilic, which allows gaseous H2 to be directly stored inside, thus significantly increasing the H2 concentration around the palladium nanoparticles (NPs). At the same time, GDY nanospheres also alter the electronic structure of the Pd NPs via a strong d-π interaction. Combining these two roles of GDY, allows the hydrogenation of benzaldehyde to proceed under ambient H2 pressure in water, with an impressive 4.3-fold enhancement compared to the unmodified Pd/mSiO2 catalyst. This study demonstrates a new role of GDY in constructing wettability matched catalysts for gas-liquid-solid tri-phase reactions.

High-Performance Heterogeneous Thermocatalysis Caused by Catalyst Wettability Regulation.

Catalyst wettability regulation has emerged as an attractive approach for high catalytic performance for the past few years. By introducing appropriate wettability, the molecule diffusion of reactants and products can be enhanced, leading to high activity. Besides this, undesired molecules are isolated for high selectivity of target products and long-term stability of catalyst. Herein, we summarize wettability-induced high-performance heterogeneous thermocatalysis in recent years, including hydrophilicity, hydrophobicity, hybrid hydrophilicity-hydrophobicity, amphiphilicity, and superaerophilicity. Relevant reactions are further classified and described according to the reason for the performance improvement. It should be pointed out that studies of utilizing superaerophilicity to improve heterogeneous thermocatalytic performance have been included for the first time, so this is a comparatively comprehensive review in this field as yet.

Unprecedentedly high activity and selectivity for hydrogenation of nitroarenes with single atomic Co1-N3P1 sites.

Transition metal single atom catalysts (SACs) with M1-Nx coordination configuration have shown outstanding activity and selectivity for hydrogenation of nitroarenes. Modulating the atomic coordination structure has emerged as a promising strategy to further improve the catalytic performance. Herein, we report an atomic Co1/NPC catalyst with unsymmetrical single Co1-N3P1 sites that displays unprecedentedly high activity and chemoselectivity for hydrogenation of functionalized nitroarenes. Compared to the most popular Co1-N4 coordination, the electron density of Co atom in Co1-N3P1 is increased, which is more favorable for H2 dissociation as verified by kinetic isotope effect and density functional theory calculation results. In nitrobenzene hydrogenation reaction, the as-synthesized Co1-N3P1 SAC exhibits a turnover frequency of 6560 h-1, which is 60-fold higher than that of Co1-N4 SAC and one order of magnitude higher than the state-of-the-art M1-Nx-C SACs in literatures. Furthermore, Co1-N3P1 SAC shows superior selectivity (>99%) toward many substituted nitroarenes with co-existence of other sensitive reducible groups. This work is an excellent example of relationship between catalytic performance and the coordination environment of SACs, and offers a potential practical catalyst for aromatic amine synthesis by hydrogenation of nitroarenes.

Direct Observation of Metal Oxide Nanoparticles Being Transformed into Metal Single Atoms with Oxygen-Coordinated Structure and High-Loadings.

Direct conversion of bulk metal or nanoparticles into metal single atoms under thermal pyrolysis conditions is a highly efficient and promising strategy to fabricate single-atom catalysts (SACs). Usually, nitrogen-doped carbon is used as the anchoring substrate to capture the migrating metal ion species at high temperatures, and stable isolated SACs with nitrogen coordination are formed during the process. Herein, we report unexpected oxygen-coordinated metal single-atom catalysts (Fe-, Co-, Ni-, Mn-SACs) with high loadings (above 10 wt %) through direct transformation of metal oxide nanoparticles (Fe-, Co-, Ni-, Mn-NPs) in an inert atmosphere at 750 °C for 2 h. The atomic dispersion of metal single atoms and their coordinated structures were confirmed by aberration-corrected scanning transmission electron microscopy and X-ray absorption fine structures. In addition, the dynamic process of nanoparticles to atoms was directly observed by in situ transmission electron microscopy. The as-prepared Fe SAC exhibited high activity and superior selectivity for catalytic oxidation of benzene to phenol with hydrogen peroxide.

Integration of Metal Single Atoms on Hierarchical Porous Nitrogen-Doped Carbon for Highly Efficient Hydrogenation of Large-Sized Molecules in the Pharmaceutical Industry.

Single-atom catalysts (SACs) often exhibit superior activity and selectivity in heterogeneous catalysis because of their maximized atom utilization and unique coordination environments. However, most reported studies about SACs in heterogeneous catalysis focus on model reactions with simple molecules. In addition, many reported single atoms are confined in microporous structures, hindering the mass transfer of molecules with large sizes, thus limiting their practical applications in industry. In this study, we report a molten salt-assisted method to synthesize metal single atoms anchored on a hierarchical porous nitrogen-doped carbon support (denoted as M1/h-NC, M includes Co, Fe, Ni, Mn, and Cu). Taking Co1/h-NC as an example, compared to the control sample which has Co single atoms being encapsulated in a microporous N-doped carbon support (denoted as Co1/m-NC), Co1/h-NC exhibits significantly higher catalytic activity in the selective hydrogenation of large-sized pharmaceutical molecules, such as nimodipine (calcium channel blocker) and 2-(3',4'-methylenedioxyphenylethyl)quinoline (antispasmodic natural alkaloid intermediate). The superior catalytic performance of Co1/h-NC is directly ascribed to the integration of the advantages of single-atom active sites and hierarchical mesoporous structure, which is beneficial for the mass transfer of molecules with large sizes and enables nearly all the Co single atoms to be accessible for catalytic reactions.

Single Chromium Atoms Supported on Titanium Dioxide Nanoparticles for Synergic Catalytic Methane Conversion under Mild Conditions.

Direct conversion of methane to value-added chemicals with high selectivity under mild conditions remains a great challenge in catalysis. Now, single chromium atoms supported on titanium dioxide nanoparticles are reported as an efficient heterogeneous catalyst for direct methane oxidation to C1 oxygenated products with H2 O2 as oxidant under mild conditions. The highest yield for C1 oxygenated products can be reached as 57.9 mol molCr -1 with selectivity of around 93 % at 50 °C for 20 h, which is significantly higher than those of most reported catalysts. The superior catalytic performance can be attributed to the synergistic effect between single Cr atoms and TiO2 support. Combining catalytic kinetics, electron paramagnetic resonance, and control experiment results, the methane conversion mechanism was proposed as a methyl radical pathway to form CH3 OH and CH3 OOH first, and then the generated CH3 OH is further oxidized to HOCH2 OOH and HCOOH.

Preparation of Ga2O3 Doped Sulfonated Tin Oxides as a Highly Active and Recyclable Heterogeneous Solid Acid Catalyst for Aldol Reactions.

Ga2O3 doped sulfonated tin oxide catalysts were prepared via co-condensation method in ethanol solvent, followed by sulfonation and calcination. The samples were characterized by isothermal nitrogen adsorption/desorption, powder X-ray diffraction (XRD), thermal gravimetric analysis (TG), Raman spectra and DRIFT spectra. The number of acid sites on the catalysts was measured with the potentiometric titration of butyl amine. The results showed that the addition of small amounts of Ga2O3 to sulfonated tin oxide resulted in an enhanced acid site density, which makes Ga2O3 doped sulfonated tin oxide catalysts highly active for aldol reactions. The catalyst containing 1.5% Ga2O3 exhibited much higher activity than those of SO4²-/SnO2, SO4²-/ZrO2 and H3PO4 in aldol condensation of prenal and prenol for citral precursor, which is a important in fragrance industry. Besides the high activity, the catalyst also exhibited good recyclability, making 1.5% GST an efficient and promising solid catalyst for aldol reactions.

N-Doped carbon nanofibers derived from bacterial cellulose as an excellent metal-free catalyst for selective oxidation of arylalkanes.

N-Doped carbon nanofibers derived from one-step pyrolysis of low-cost bacterial cellulose with the assistance of urea were reported. Owing to their interconnected nanofibrous structure and high specific surface area as well as high N doping, they exhibited excellent catalytic performance for selective oxidation of arylalkanes even with O2 as an oxidant in aqueous solution.

Controllable Synthesis of Multiheteroatoms Co-Doped Hierarchical Porous Carbon Spheres as an Ideal Catalysis Platform.

The synthesis of porous carbon spheres with hierarchical porous structures coupled with the doping of heteroatoms is particularly important for advanced applications. In this research, a new route for efficient and controllable synthesis of hierarchical porous carbon spheres co-doped with nitrogen, phosphorus, and sulfur (denoted as NPS-HPCs) was reported. This new approach combines in situ polymerization of hexachlorocyclophosphazene and 4,4'-sulfonyldiphenol with the self-assembly of colloidal silica nanoparticles (SiO2 NPs). After pyrolysis and subsequent removal of the SiO2 NPs, the resulting NPS-HPCs possess a high surface area (960 m2/g) as well as homogeneously distributed N, P, and S heteroatoms. The NPS-HPCs are shown to be an ideal support for anchoring highly dispersed and uniformly sized noble metal NPs for heterogeneous catalysis. As a proof of concept, Pd NPs are loaded onto the NPS-HPCs using only methanol as a reductant at room temperature. The prepared Pd/NPS-HPCs are shown to exhibit high activity, excellent stability, and recyclability for hydrogenation of nitroarenes.

Enhancing reaction rate in a Pickering emulsion system with natural magnetotactic bacteria as nanoscale magnetic stirring bars.

Pickering emulsion is emerging as an advanced platform for catalysis because of the large oil/water interface area for reaction and its superior efficiency. How to enhance the mass transportation within the micro-droplets is the biggest obstacle in further improving the efficiency of the Pickering emulsion system. In this study, we propose and solve this problem for the first time using natural magnetotactic bacteria as nanoscale magnetic stirring bars, which can be encapsulated into each micro-droplet and used to stir the solution to accelerate the mass transportation under an external magnet, and thus significantly enhance the reaction rate of Pickering emulsion. Taking the epoxidation of cyclooctene in the Pickering emulsion system as a demonstration, the reaction rate was enhanced three times with nanoscale magnetic stirring bars compared to that of traditional Pickering emulsion, and was even thirty times higher than that of conventional stirrer-driven biphasic systems. We envision that this strategy will bring biphasic reactions with fundamental innovations toward more green, efficient and sustainable chemistry.

Chiral Metal-Organic Framework Hollow Nanospheres for High-Efficiency Enantiomer Separation.

Chiral ZIF-8 hollow nanospheres with d-histidine as part of chiral ligands (denoted as H-d-his-ZIF-8) were prepared for separation of (±)-amine acids. Compared to bulk d-his-ZIF-8 without a hollow cavity, the prepared H-d-his-ZIF-8 showed 15 times higher separation capacity and higher ee values of 90.5 % for alanine, 95.2 % for glutamic acid and 92.6 % for lysine, respectively.

Extremely low loading of Ru species on hydroxyapatite as an effective heterogeneous catalyst for olefin epoxidation.

We report a new class promising heterogeneous catalyst for olefin epoxidation based on 0.05 wt% Ru species supported on hydroxyapatite, which was prepared through a simple cation-exchange process between RuCl3·nH2O and hydroxyapatite. The new catalyst showed high activity, excellent selectivity and good recyclability for various olefins in the presence of molecular oxygen and iso-butyraldehyde as co-oxidants.