Construction of Nickel Single Atoms by Using the Inherent Confined Space in Template-Occupied Mesoporous Silica.

Due to their maximum atomic use of metal sites, single-atom catalysts (SACs) exhibit excellent catalytic activity in a variety of reactions. Although many techniques have been reported for the production of SACs, the construction of single atoms through a convenient strategy is still challenging. Here, we provide a facile method to prepare nickel SACs by utilizing the inherent confined space between the template and silica walls in template-occupied mesoporous silica KIT-6 (TOK). After the introduction of nickel-containing precursors into the inherent confined space of the TOK by solid-phase grinding, Ni SACs can be produced promptly during calcination. Single Ni atoms create a covalent Ni-O-Si structure in the TOK, as indicated by density functional theory (DFT) calculations and experimental data. This synthetic approach is easy to scale up, and 10 g of sample can be effortlessly synthesized using ball milling. The resultant Ni SACs were applied to the oxygen evolution reaction and exhibited higher catalytic activity and stability than the comparative sample synthesized in the absence of confined space.

Stable Mg Single-Atom Solid Base Catalysts Anchored on Metal-Organic Framework-Derived Nitrogen-Doped Carbon.

Solid base catalysts are widely used in the chemical industry owing to their advantages of environmental friendliness and easy separation. However, their application is limited by basic site aggregation and poor stability. In this study, we report the preparation of magnesium (Mg) single-atom catalysts with high activity and stability by a sublimation-trapping strategy. The Mg net was sublimated as Mg vapor at 620 °C, subsequently transported through argon, and finally trapped on the defects of nitrogen-doped carbon derived from metal-organic framework ZIF-8, producing Mg1/NC. Because of the atomically dispersed Mg sites, the obtained Mg1/NC exhibits high catalytic activity and stability for Knoevenagel condensation of benzaldehyde with malononitrile, which is a typical base-catalyzed reaction. The Mg1/NC catalyst achieves a high efficiency with a turnover frequency of 49.6 h-1, which is much better than that of the traditional counterpart MgO/NC (7.7 h-1). In particular, the activity of Mg1/NC shows no decrease after five catalytic cycles, while that of MgO/NC declines due to the instability of basic sites.

Transition Metal Single Atoms Constructed by Using Inherent Confined Space.

Single-atom catalysts (SACs) show expressively enhanced activity toward diverse reactions due to maximized atomic utilization of metal sites, while their facile, universal, and massive preparation remains a pronounced challenge. Here we report a facile strategy for the preparation of SACs by use of the inherent confined space between the template and silica walls in template-occupied mesoporous silica SBA-15 (TOS). Different transition metal precursors can be introduced into the confined space readily by grinding, and during succeeding calcination single atoms are constructed in the form of M-O-Si (M = Cu, Co, Ni, and Zn). In addition to the generality, the present strategy is easy to scale up and can allow the synthesis of 10 g of SACs in one pot through ball milling. The Cu SAC has been applied for CO2 cycloaddition of epichlorohydrin, and the activity is obviously higher than the counterpart prepared without confined space and various reported Cu-containing catalysts.

Catalytically Stable Potassium Single-Atom Solid Superbases.

Solid superbases can catalyze diverse reactions under mild conditions, while they suffer from aggregation of basic sites and poor stability during recycling. Here we report a new generation of solid superbases derived from K single atoms (SAs) prepared by a tandem redox strategy. The initial redox reaction takes place between base precursor KNO3 and graphene support, producing K2 O at 400 °C. Further increasing the temperature to 800 °C, the graphene reduces K2 O to K anchored by its vacancies, leading to the generation of K SAs (denoted as K1 /G). The source of basicity in the K1 /G is K SAs, and neighboring single atoms (NSAs) possess superbasicity, which is different from conventional basicity originated from oxygen and nitrogen atoms. Due to the superbasicity as well as high dispersion and anchoring of basic sites, the K1 /G shows excellent catalytic activity and stability in transesterification reaction, which is much superior to the reported catalysts.

Generation of Strong Basicity in Metal-Organic Frameworks: How Do Coordination Solvents Matter?

Solid strong bases with an ordered pore structure (OPS-SSBs) have attracted much attention because of their high catalytic activity and shape selectivity as heterogeneous catalysts in various reactions. Nevertheless, high temperatures are required to fabricate OPS-SSBs by using traditional methods. Herein, we report for the first time that the coordination solvents affect basicity generation in metal-organic frameworks (MOFs) greatly and that strong basicity can be formed at comparatively low temperatures. A typical MOF, MIL-53, was employed, and three different solvents, namely, water, methanol, and N,N-dimethylformamide (DMF), were coordinated, respectively, by means of solvent exchange. Thermogravimetry-mass spectrometer analysis shows that the conversion temperature of base precursor KNO3 is quite different on MIL-53 coordinated with different solvents. The conversion of KNO3 to basic sites takes place at 350, 300, and 250 °C on MIL-53 coordinated with water, methanol, and DMF, respectively. It is fascinating to observe the generation temperature of strongly basic sites at 250 °C, which is noticeably lower than that on various supports, such as mesoporous silica SBA-15 (600 °C), zeolite Y (700 °C), and metal oxide ZrO2 (730 °C). This is due to the redox interaction between coordination solvents and KNO3, leading to a significant decrease in the temperature for KNO3 conversion. Consequently, OPS-SSBs were prepared successfully with an ordered pore structure and strong basicity. The obtained OPS-SSBs show good shape selectivity in Knoevenagel condensation of aromatic aldehydes with different active methylene compounds. Moreover, these solid bases are highly active in the synthesis of dimethyl carbonate through transesterification reaction. This work might open up a new avenue for the fabrication of various functional materials at low temperatures through redox interactions.

Hybridization with Ti3C2Tx MXene: An Effective Approach to Boost the Hydrothermal Stability and Catalytic Performance of Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) have attracted increasing research enthusiasm owing to their tunable functionality, diverse structure characteristics, and large surface area. However, poor hydrothermal stability restricts the utilization of some MOFs in practical applications. Our work aims at improving the hydrothermal stability of a representative MOF, namely, HKUST-1, by incorporating a two-dimensional material Ti3C2Tx MXene for the first time. A new type of hybrid material is synthesized through the hybridization of HKUST-1 and Ti3C2Tx, and the obtained hybrids show improved hydrothermal stability as well as catalytic performance. The porosity of hybrids is enhanced when incorporating an appropriate amount of Ti3C2Tx, and the surface area can reach 1380 m2·g-1, while the pristine HKUST-1 is 1210 m2·g-1. After the hydrothermal treatment (hot water vapor, 70 °C), the structure of hybrid materials maintains well, while the framework of HKUST-1 is severely destroyed. When catalyzing the ring-opening reaction of styrene oxide, the conversion reaches 76.7% only for 20 min, which is much higher than that of pure HKUST-1 (23.1% for 20 min). More importantly, the catalytic activity could recover without loss even after six cycles. Our hybrid materials are promising in practical catalytic applications due to their excellent hydrothermal stability, catalytic activity, and reusability.

Enhancing oxidation resistance of Cu(I) by tailoring microenvironment in zeolites for efficient adsorptive desulfurization.

The zeolite Cu(I)Y is promising for adsorptive removal of thiophenic sulfur compounds from transportation fuels. However, its application is seriously hindered by the instability of Cu(I), which is easily oxidized to Cu(II) even under atmospheric environment due to the coexistence of moisture and oxygen. Here, we report the adjustment of zeolite microenvironment from hydrophilic to superhydrophobic status by coating polydimethylsiloxane (yielding Cu(I)Y@P), which isolates moisture entering the pores and subsequently stabilizes Cu(I) despite the presence of oxygen. Cu(I) in Cu(I)Y@P is stable upon exposure to humid atmosphere for 6 months, while almost all Cu(I) is oxidized to Cu(II) in Cu(I)Y for only 2 weeks. The optimized Cu(I)Y@P material after moisture exposure can remove 532 µmol g-1 of thiophene and is much superior to Cu(I)Y (116 µmol g-1), regardless of similar uptakes for unexposed adsorbents. Remarkably, Cu(I)Y@P shows excellent adsorption capacity of desulfurization for water-containing model fuel.

Significant Decrease in Activation Temperature for the Generation of Strong Basicity: A Strategy of Endowing Supports with Reducibility.

Mesoporous solid strong bases are quite attractive due to their good catalytic performance for applications as environmentally friendly catalysts in various reactions. However, pretty harsh conditions are usually compulsory for the fabrication of strong basicity by using traditional thermal activation (e.g., 700 °C for the activation of base precursor KNO3 supported on mesoporous Al2O3). This is energy intensive and harmful to the mesoporous structure. In this study, we report a strategy of endowing supports with reducibility (ESWR) by doping low-valence Cr3+ into mesoporous Al2O3, so that the activation temperature for basicity generation is decreased significantly. Fascinatingly, KNO3 on mesoporous Al2O3 can be motivated to basic sites completely at the temperature of 400 °C via the ESWR strategy, which is much lower than the conventional thermal activation (700 °C). We have demonstrated that the redox reciprocity between KNO3 and Cr3+ is responsible for the low-temperature conversion, and Cr6+ is formed quantitatively as the oxidation product. The obtained solid bases possessing ordered mesostructure and strong basicity provide promising candidates for base-catalyzed synthesis of dimethyl carbonate via transesterification. The catalytic activity is obviously higher than a typical solid base like MgO as well as a series of reported basic catalysts containing alkali metal and alkaline-earth metal oxides.