Insights into the Acidic Site in Manganese Oxide in Terms of the Sulfur and Water Tolerance of Low-Temperature NH3 Selective Catalytic Reduction.

A critical constraint impeding the utilization of Mn-based oxide catalysts in NH3 selective catalytic reduction (NH3-SCR) is their inadequate resistance to water and sulfur. This vulnerability primarily arises from the propensity of SO2 to bind to the acidic site in manganese oxide, resulting in the formation of metal sulfate and leading to the irreversible deactivation of the catalyst. Therefore, gaining a comprehensive understanding of the detrimental impact of SO2 on the acidic sites and elucidating the underlying mechanism of this toxicity are of paramount importance for the effective application of Mn-based catalysts in NH3-SCR. Herein, we strategically modulate the acidity of the manganese oxide catalyst surface through the incorporation of Ce and Nb. Comprehensive analyses, including thermogravimetry, NH3 temperature-programmed desorption, in situ diffused reflectance infrared Fourier transform spectroscopy, and density functional theory calculations, reveal that SO2 exhibits a propensity for adsorption at strongly acidic sites. This mechanistic understanding underscores the pivotal role of surface acidity in governing the sulfur resistance of manganese oxide.

Construction of Asymmetric Filler Density Mixed-Matrix MOF Membranes via Liquid-Phase Ion Activation for Advanced Oxidation Processes.

Mixed-matrix membrane (MMM) reactors incorporating metal-organic framework (MOF) fillers have significant applications in fields such as separation, catalysis, and chiral resolution. However, the traditional method of directly mixing MOF fillers with polymers results in a symmetric structure where most of the MOF fillers are uniformly distributed across the membrane reactor's cross-section. During usage, this leads to a pronounced trade-off between flux and efficiency and the waste of the MOF, as the rich pore characteristics and active sites of MOFs are not fully utilized. In this study, we propose a liquid-phase ion activation strategy that enables the in situ formation of a uniform and densely packed MOF shell layer on the membrane surface during the phase inversion process of MMM fabrication. This asymmetric density distribution of the MOF-based MMM reactor selectively induces the generation of considerable nonradical 1O2 in the peroxomonosulfate (PMS) system, demonstrating superior catalytic degradation performance against antibiotics like TC and dye molecules (with a flux of 1880 L m-2 h-1 and a Kapp value of 648 min-1), as well as outstanding cycling stability and environmental tolerance. This discovery sheds light on the design and engineering of composite membrane materials and applications for advanced oxidation processes in water purification.

Engineering of Pore Design and Oxygen Vacancy on High-Entropy Oxides by a Microenvironment Tailoring Strategy.

High-entropy oxides (HEOs) exhibit abundant structural diversity due to cationic and anionic sublattices with independence, rendering them superior in catalytic applications compared to monometallic oxides. Nevertheless, the conventional high-temperature calcination approach undermines the porosity and reduces the exposure of active sites (such as oxygen vacancies, OVs) in HEOs, leading to diminished catalytic efficiency. Herein, we fabricate a series of HEOs with a large surface area utilizing a microenvironment modulation strategy (m-NiMgCuZnCo: 86 m2/g, m-MnCuCoNiFe: 67 m2/g, and m-FeCrCoNiMn: 54 m2/g). The enhanced porosity in m-NiMgCuZnCo facilitates the presentation of numerous OVs, exhibiting an exceptional catalytic performance. This tactic creates inspiration for designing HEOs with rich porosity and active species with vast potential applications.

Embedding Hierarchical Pores by Mechanochemistry in Carbonates with Superior Chemoselective Catalysis and Stability.

Hierarchical porosity of carbonates can facilitate their performance in massive applications as compared to their corresponding bulk samples. Traditional solution-based precipitation is typically utilized to fabricate porous carbonates. However, this tactic is generally employed under humid conditions, which demand soluble metal precursors, solvents, and extended dry periods. A salt-assisted mechanochemistry is exploited in contemporary work to settle the shortcomings. Enlighted by solid-state technology, this approach eliminates the utilization of solvents, and the process of ball milling can create pores in 5 min. A range of highly porous carbonates and their derivatives are acquired, with several materials surpassing recording surface areas (e.g., H-CaCO3: 108 m2/g, SrCO3: 125 m2/g, BaCO3: 172 m2/g, Pd/H-CaCO3 catalyst: 101 m2/g). The results display that Pd/H-CaCO3 shows superior catalytic efficiency in the synthesis of aniline (turnover frequency [TON] = 1.33 × 104/h-1, yield ≥ 99%, and recycle stability: 11 cycles) and dye degradation. Combining mechanochemistry and salt-assisted tactic provides a facile and efficient pathway for processing porous materials.

Green and Large-Scale Preparation of Chiral Metal-Organic Frameworks via Mechanochemistry.

It is a significant challenge to construct chiral metal-organic frameworks (CMOFs) by developing a facile and green preparation strategy. In this work, CMOFs were first synthesized via a mechanochemical process by combining a truncated mixed ligand strategy and defect engineering theory. The simple, green, and rapid construction strategy could solvent-freely harvest gram-scale CMOFs with a hierarchical micro/mesoporous structure. The as-synthesized CMOFs were evaluated by Aldol asymmetric catalysis and exhibited excellent catalytic performance (conversion was up to 97.1%, the ee value was 44.3%, and the activity was still good after 5 cycles).

Self-Stirring Microcatalysts: Large-Scale, High-Throughput, and Controllable Preparation and Application.

Herein, we introduce a strategy to develop a kind of unprecedented microcatalyst, which owns self-stirring and catalytic performance based on pneumatic printing and magnetic field induction technology. A spindle-shaped microcatalyst based on metal-organic frameworks (MOFs) with a certain aspect ratio and size can be obtained by tuning the printing parameters and the intensity of the magnetic field. One nozzle can print 18 000 microcatalysts per hour, which provides a prerequisite for the realization of large-scale production in the industrial field. Furthermore, this strategy can be widely applied to a variety of other heterogeneous catalysts, such as mesoporous SiO2, zeolite, metallic oxide, and so on. To demonstrate the superiority of the printed catalyst, the series of printed microcatalysts were evaluated by various catalytic reactions including liquid-phase hydrogenation, microdroplet dye-fading, and photocatalytic degradation in microreactor, all of which exhibited excellent catalytic performance.

Chiral Yolk-Shell MOF as an Efficient Nanoreactor for Asymmetric Catalysis in Organic-Aqueous Two-Phase System.

It remains a great challenge to introduce large and efficient homogeneous asymmetric catalysts into MOFs and other microporous materials as well as retain their degrees of freedom. Herein, a new heterogeneous strategy of homogeneous chiral catalysts is proposed, that is, to construct a yolk-shell MOFs-confined, large-size, and highly efficient homogeneous chiral catalyst, which can be used as a nanoreactor for asymmetric catalytic reactions.

Constructing an efficient electrocatalyst for water oxidation: an Fe-doped CoO/Co catalyst enabled by in situ MOF growth and a solvent-free strategy.

The development of non-precious metal electrocatalysts with high activity for the oxygen evolution reaction (OER) is a crucial and challenging task. In this work, we proposed a solvent-free in situ metal-organic framework (MOF) growth strategy for the fabrication of an Fe-doped CoO/Co electrocatalyst. This approach not only partially granted the MOF's porous structure to the catalyst but also resulted in a tighter combination between the Co metal and CoO, thereby enhancing its electrical conductivity. Furthermore, this method enabled the Fe species to be more uniformly dispersed on CoO/Co, which significantly exposed more active sites for efficient electrocatalysis. The entire synthesis process was solvent-free, except for a small amount of water and ethanol used during catalyst washing. The as-synthesized Fe-CoO/Co electrocatalyst exhibited superior OER activity on a glass carbon electrode, with η = 276 mV at a current density of 10 mA cm-2, even higher than that of the commercial precious IrO2/C catalyst. Additionally, it was also extended to prepare a Ni-doped CoO/Co electrocatalyst by the same procedure with satisfactory OER performance. This work presents a new preparation approach for MOF-derived catalysts with potential applications in energy conversion and beyond.

Defect Engineering of High-Entropy Oxides for Superior Catalytic Oxidation Performance.

High-entropy oxides (HEOs) are crucial in various fields (power storage/conversion, electronic devices, and catalysis) owing to their adjustable structural characteristics, fabulous stability, and massive components. However, the current strategies for synthesizing HEOs suffer from low surface area and limited active sites. Herein, we present a salt-assisted strategy with remarkable universality for the preparation of HEOs with high surface area [e.g., HP-(FeCrCoNiCu)xOy: 59 m2/g, HP-(ZnMgNiCuCo)xOy: 49 m2/g, and HP-(CrMnFeNiZn)xOy: 11 m2/g], where HP means high porosity. Especially, HP-(FeCrCoNiCu)xOy with rich-oxygen vacancies promotes catalytic efficiency for hydrocarbon and alcohol oxidation owing to its hierarchical texture and massive oxygen vacancies. Furthermore, density functional theory is utilized to well illustrate the relationship of the structure and catalytic efficiency within the catalysts. This work offers realistic pathway for the large-scale application of HEOs in catalytic areas.

Step by Step Construction of Multifunctional Hollow Double Shell MNPs@MOF as a Powerful Tandem/Cascade Catalyst.

The development of efficient heterogeneous catalysts for one-pot tandem/cascade synthesis of imines remains meaningful and challenging. Herein, we constructed an Au/MOF catalyst featured hollow and double MOF shell nanostructure. Owing to its structural merits and acid-basic nature, the as-synthesized Void|(Au)ZIF-8|ZIF-8 catalyst exhibited an enhanced synergistically catalytic performance for tandem catalytic synthesis of imines from benzyl alcohol and aniline under air atmosphere and solvent-free condition. Its 170.16 h-1 of turnover frequency (TOF) was 2.5 times higher than that of the reported catalyst with the highest TOF value.

Fabrication of Magnetic Pd/MOF Hollow Nanospheres with Double-Shell Structure: Toward Highly Efficient and Recyclable Nanocatalysts for Hydrogenation Reaction.

MNPs@MOF catalysts obtained by encapsulating metal nanoparticles (NPs) into metal-organic frameworks (MOFs) show fascinating performance in heterogeneous catalysis. The improvement of catalytic activity and reusability of MNPs@MOF catalysts has been a great challenge for a long time. Herein, we demonstrate well-designed Pd/MOFs, featuring hollow double-shell structure and magnetic property, exhibiting high reusability, efficient catalytic activity, and size selectivity for hydrogenation reaction. The as-synthesized Pd/MOF, denoted as Void nFe3O4@Pd/ZIF-8@ZIF-8, possesses diverse functional structural features. The hollow cavity can improve mass transfer; superparamagnetic Fe3O4 NPs embedded in the inner MOF shell can enhance the separation and recyclability; Pd NPs are highly dispersed in the matrix of the inner MOF shell, and the outer MOF shell acts as a protector to prevent the leaching of Pd NPs and a sieve to achieve size selectivity. As a proof of concept, the Void nFe3O4@Pd/ZIF-8@ZIF-8 catalyst exhibited excellent performance for the hydrogenation of styrene at room temperature. The activity only reduced 10% after 20 cycles for the higher conversions (>90%), and the lower conversion only decreased 3.6% (from 32.5 to 28.9% conversion) after twenty consecutive cycles, indicating the good and intrinsic reusability of the catalyst. The proposed structure in this work provides a strategy to effectively improve the reusability of MNPs@MOF catalysts, which would increase their practical applications.