Ligand-Bound CO2 as a Nonclassical Route toward Efficient Photocatalytic CO2 Reduction with a Ni N-Confused Porphyrin.

Implementing the synergistic effects between the metal and the ligand has successfully streamlined the energetics for CO2 activation and gained high catalytic activities, establishing the important breakthroughs in photocatalytic CO2 reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N-H group. It is readily deprotonated and exists in an anion form during catalysis. Owing to this functional site, NiNCP gave rise to an outstanding turnover number (TON) as high as 217,000 with a 98% selectivity for CO2 reduction to CO, while the parent Ni(II) porphyrin (NiTPP) was found to be nearly inactive. Our mechanistic analysis revealed a nonclassical reaction pattern where CO2 was effectively activated via the attack of the Lewis-basic ligand. The resulting ligand-bound CO2 adduct could be further reduced to produce CO. This new metal-ligand synergistic effect is anticipated to inspire the design of highly active catalysts for small molecule activations.

Atomically Dispersed Fe-Cu Dual-Metal Sites Synergistically Boost Carbonylation of Methane.

The production of acetic acid, an important industrial chemical traditionally obtained through the carbonylation of methanol using noble metal-based homogeneous catalysts, encounters challenges arising from high equipment costs and sustainability concerns. The direct liquid-phase oxidative carbonylation of methane emerges as a promising alternative, capitalizing on abundant natural gas resources and featuring a potentially mild and straightforward process. However, most catalysts proposed for this process suffer from low acetic acid yields due to the scarcity of active sites and the swift generation of C1 oxygenates, posing difficulties for subsequent carbonylation and impeding their industrial feasibility. Herein, we report a highly efficient 0.1Cu/Fe-HZ5-TF catalyst featuring exclusively mononuclear Fe and Cu anchored in the ZSM-5 channels. Under optimized conditions, the catalyst achieved an unprecedented acetic acid yield of 40.5 mmol gcat-1 h-1 at 50 °C, surpassing the previous maximum (12.0 mmol gcat-1h-1) by more than threefold. Comprehensive characterization, isotope-labeled experiments and DFT calculations reveal that the homogeneous mononuclear Fe sites are responsible for the activation and oxidation of methane, while the neighboring Cu sites play a key role in retarding the oxidation process. This synergistic action promotes C-C coupling, resulting in the efficient synthesis of acetic acid.

Rim-Based Binding of Perfluorinated Acids to Pillararenes Purifies Water.

Per- and polyfluoroalkyl substances (PFAS) pose a rapidly increasing global problem as their widespread use and high stability lead worldwide to water contamination, with significant detrimental health effects.[1] Supramolecular chemistry has been invoked to develop materials geared towards the specific capture of PFAS from water,[2] to reduce the concentration below advisory safety limits (e.g., 70 ng/L for the sum of perfluorooctane sulfonic acid, PFOS and perfluorooctanoic acid, PFOA). Scale-up and use in natural waters with high PFAS concentrations has hitherto posed a problem. Here we report a new type of host-guest interaction between deca-ammonium-functionalized pillar[5]arenes (DAF-P5s) and perfluoroalkyl acids. DAF-P5 complexes show an unprecedented 1 : 10 stoichiometry, as confirmed by isothermal calorimetry and X-ray crystallographic studies, and high binding constants (up to 106 M-1) to various polyfluoroalkyl acids. In addition, non-fluorinated acids do not hamper this process significantly. Immobilization of DAF-P5s allows a simple single-time filtration of PFAS-contaminated water to reduce the PFOS/PFOA concentration 106 times to 15-50 ng/L level. The effective and fast (<5 min) orthogonal binding to organic molecules without involvement of fluorinated supramolecular hosts, high breakthrough capacity (90 mg/g), and robust performance (>10 regeneration cycles without decrease in performance) set a new benchmark in PFAS-absorbing materials.

Asymmetric Sites on the ZnZrOx Catalyst for Promoting Formate Formation and Transformation in CO2 Hydrogenation.

The role of formate species for CO2 hydrogenation is still under debate. Although formate has been frequently observed and commonly proposed as the possible intermediate, there is no definite evidence for the reaction of formate species for methanol production. Here, formate formation and conversion over the ZnZrOx solid solution catalyst are investigated by in situ/operando diffuse reflectance infrared Fourier transform spectroscopy-mass spectroscopy (DRIFTS-MS) coupled with density functional theory (DFT) calculations. Spectroscopic results show that bidentate carbonate formed from CO2 adsorption is hydrogenated to formate on Zn-O-Zr sites (asymmetric sites), where the Zn site is responsible for H2 activation and the Zr site is beneficial for the stabilization of reaction intermediates. The asymmetric Zn-O-Zr sites with adjacent and inequivalent features on the ZnZrOx catalyst promote not only formate formation but also its transformation. Both theoretical and experimental results demonstrate that the origin of the excellent performance of the ZnZrOx catalyst for methanol formation is associated with the H2 heterolytic cleavage promoted by the asymmetric Zn and Zr sites.

Maximizing Active Fe Species in ZSM-5 Zeolite Using Organic-Template-Free Synthesis for Efficient Selective Methane Oxidation.

The selective oxidation of CH4 in the aqueous phase to produce valuable chemicals has attracted considerable attention due to its mild reaction conditions and simple process. As the most widely studied catalyst for this reaction, Fe-ZSM-5 demonstrates high intrinsic activity and selectivity; however, Fe-ZSM-5 prepared using conventional methods has a limited number of active Fe sites, resulting in low CH4 conversion per unit mass of the catalyst. This study reports a facile organic-template-free synthesis strategy that enables the incorporation of more Fe into the zeolite framework with a higher dispersion degree compared to conventional synthesis methods. Because framework Fe incorporated in this way is more readily transformed into isolated extra-framework Fe species under thermal treatment, the overall effect is that Fe-ZSM-5 prepared using this method (Fe-HZ5-TF) has 3 times as many catalytically active sites as conventional Fe-ZSM-5. When used for the selective oxidation of CH4 with 0.5 M H2O2 at 75 °C, Fe-HZ5-TF produced a high C1 oxygenate yield of 109.4 mmol gcat-1 h-1 (a HCOOH selectivity of 91.1%), surpassing other catalysts reported to date. Spectroscopic characterization and density functional theory calculations revealed that the active sites in Fe-HZ5-TF are mononuclear Fe species in the form of [(H2O)3Fe(IV)═O]2+ bound to Al pairs in the zeolite framework. This differs from conventional Fe-ZSM-5, where binuclear Fe acts as the active site. Analysis of the catalyst and product evolution during the reaction suggests a radical-driven pathway to explain CH4 activation at the mononuclear Fe site and subsequent conversion to C1 oxygenates.

Revealing Active Sites and Reaction Pathways in Methane Non-Oxidative Coupling over Iron-Containing Zeolites.

Non-oxidative coupling of methane is a promising route to obtain ethylene directly from natural gas. We synthesized siliceous [Fe]zeolites with MFI and CHA topologies and found that they display high selectivity (>90 % for MFI and >99 % for CHA) to ethylene and ethane among gas-phase products. Deactivated [Fe]zeolites can be regenerated by burning coke in air. In situ X-ray absorption spectroscopy demonstrates that the isolated Fe3+ centers in zeolite framework of fresh catalysts are reduced during the reaction to the active sites, including Fe2+ species and Fe (oxy)carbides dispersed in zeolite pores. Photoelectron photoion coincidence spectroscopy results show that methyl radicals are the reaction intermediates formed upon methane activation. Ethane is formed by methyl radical coupling, followed by its dehydrogenation to ethylene. Based on the observation of intermediates including allene, vinylacetylene, 1,3-butadiene, 2-butyne, and cyclopentadiene over [Fe]MFI, a reaction network is proposed leading to polyaromatic species. Such reaction intermediates are not observed over the small-pore [Fe]CHA, where ethylene and ethane are the only gas-phase products.

Ground-state properties of the narrowest zigzag graphene nanoribbon from quantum Monte Carlo and comparison with density functional theory.

By means of quantum Monte Carlo (QMC) calculations from first-principles, we study the ground-state properties of the narrowest zigzag graphene nanoribbon with an infinite linear acene structure. We show that this quasi-one-dimensional system is correlated and its ground state is made of localized π electrons whose spins are antiferromagnetically ordered. The antiferromagnetic (AFM) stabilization energy [36(3) meV per carbon atom] and the absolute magnetization [1.13(0.11) µB per unit cell] predicted by QMC are sizable, and they suggest the survival of antiferromagnetic correlations above room temperature. These values can be reproduced to some extent by density functional theory (DFT) within the DFT+U framework or by using hybrid functionals. Based on our QMC results, we then provide the strength of Hubbard repulsion in DFT+U suitable for this class of systems.

Sulfur-Phenolate Exchange: SuFEx-Derived Dynamic Covalent Reactions and Degradation of SuFEx Polymers.

The products of the SuFEx reaction between sulfonimidoyl fluorides and phenols, sulfonimidates, are shown to display dynamic covalent chemistry with other phenols. This reaction was shown to be enantiospecific, finished in minutes at room temperature in high yields, and useful for both asymmetric synthesis and sustainable polymer production. Its wide scope further extends the usefulness of SuFEx and related click chemistries.

Phosphorus Tailors the d-Band Center of Copper Atomic Sites for Efficient CO2 Photoreduction under Visible-Light Irradiation.

Photoreduction of CO2 into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single-Cu-atom catalysts with unique Cu configurations in phosphorus-doped carbon nitride (PCN), namely, Cu1 N3 @PCN and Cu1 P3 @PCN were fabricated via selective phosphidation, and tested in visible light-driven CO2 reduction by H2 O without sacrificial agents. Cu1 N3 @PCN was exclusively active for CO production with a rate of 49.8 µmolCO gcat -1 h-1 , outperforming most polymeric carbon nitride (C3 N4 ) based catalysts, while Cu1 P3 @PCN preferably yielded H2 . Experimental and theoretical analysis suggested that doping P in C3 N4 by replacing a corner C atom upshifted the d-band center of Cu in Cu1 N3 @PCN close to the Fermi level, which boosted the adsorption and activation of CO2 on Cu1 N3 , making Cu1 N3 @PCN efficiently convert CO2 to CO. In contrast, Cu1 P3 @PCN with a much lower Cu 3d electron energy exhibited negligible CO2 adsorption, thereby preferring H2 formation via photocatalytic H2 O splitting.

Alizarin Grafting onto Ultrasmall ZnO Nanoparticles: Mode of Binding, Stability, and Colorant Studies.

The demand is rising for colorants that are obtained from natural resources, tolerant to industrial processing methods, and meet color quality demands. Herein, we report how relevant properties such as thermal stability and photostability of the natural colorant alizarin can be improved by grafting it onto ZnO nanoparticles (NPs), allowing application in a warm extrusion process for the fabrication of polyamide fibers. For this study, ZnO NPs (diameter 2.0 ± 0.6 nm) were synthesized and subsequently functionalized with alizarin. The alizarin-coated ZnO NPs (i.e., dyed nanoparticles, DNPs) were characterized. Thermogravimetric analysis and ultraviolet-visible (UV-vis) studies revealed that alizarin coating accounts for ∼65% (w/w) of the total mass of the DNPs. A subsequent detailed characterization with Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C cross-polarization magic angle spinning (CP-MAS) NMR, X-ray photoelectron spectroscopy (XPS), and quantum chemistry studies using various density functional theory (DFT) functionals and basis sets indicated that binding onto the ZnO NPs occurred predominantly via the catechol moiety of alizarin. Importantly, this grafting increased the thermal stability of alizarin with >100 °C, which allowed the processing of the DNPs into polyamide fibers by warm extrusion at 260 °C. Evaluation of the lightfastness of the DNP-dyed nylon fibers revealed that the changes in color quantified via the distance metric ΔE* of alizarin when embedded in a hybrid material were 2.6-fold better compared to nylon fibers that were directly dyed with alizarin. This reveals that the process of immobilization of a natural dye onto ZnO nanoparticles indeed improves the dye properties significantly and opens the way for a wide range of further studies into surface-immobilized dyes.

Phosphorus Induced Electron Localization of Single Iron Sites for Boosted CO2 Electroreduction Reaction.

Electrochemical reduction of carbon dioxide (CO2 ) into chemicals and fuels has recently attracted much interest, but normally suffers from a high overpotential and low selectivity. In this work, single P atoms were introduced into a N-doped carbon supported single Fe atom catalyst (Fe-SAC/NPC) mainly in the form of P-C bonds for CO2 electroreduction to CO in an aqueous solution. This catalyst exhibited a CO Faradaic efficiency of ≈97 % at a low overpotential of 320 mV, and a Tafel slope of only 59 mV dec-1 , comparable to state-of-the-art gold catalysts. Experimental analysis combined with DFT calculations suggested that single P atom in high coordination shells (n≥3), in particular the third coordination shell of Fe center enhanced the electronic localization of Fe, which improved the stabilization of the key *COOH intermediate on Fe, leading to superior CO2 electrochemical reduction performance at low overpotentials.

Intrinsic Facet-Dependent Reactivity of Well-Defined BiOBr Nanosheets on Photocatalytic Water Splitting.

Surface atomic arrangement and coordination of photocatalysts highly exposed to different crystal facets significantly affect the photoreactivity. However, controversies on the true photoreactivity of a specific facet in heterogeneous photocatalysis still exits. Herein, we exemplified well-defined BiOBr nanosheets dominating with respective facets, (001) and (010), to track the reactivity of crystal facets for photocatalytic water splitting. The real photoreactivity of BiOBr-(001) were evidenced to be significantly higher than BiOBr-(010) for both hydrogen production and oxygen evolution reactions. Further in situ photochemical probing studies verified the distinct reactivity is not only owing to the highly exposed facets, but dominated by the co-exposing facets, leading to an efficient spatial separation of photogenerated charges and further making the oxidation and reduction reactions separately occur with different reaction rates, which ordains the fate of the true photoreactivity.

Engineering the Protein Corona Structure on Gold Nanoclusters Enables Red-Shifted Emissions in the Second Near-infrared Window for Gastrointestinal Imaging.

The application of NIR-II emitters for gastrointestinal (GI) tract imaging remains challenging due to fluorescence quenching in the digestive microenvironment. Herein, we report that red-shifting of the fluorescence emission of Au nanoclusters (AuNCs) into NIR-II region with improved quantum yields (QY) could be achieved by engineering a protein corona structure consisting of a ribonuclease-A (RNase-A) on the particle surfaces. RNase-A-encapsulated AuNCs (RNase-A@AuNCs) displayed emissions at 1050 nm with a 1.9 % QY. Compared to rare earth and silver-based NIR-II emitters, RNase-A@AuNCs had excellent biocompatibility, showing >50-fold higher sensitivity in GI tract, and migrated homogenously during gastrointestinal peristalsis to allow visualization of the detailed structures of the GI tract. RNase-A@AuNCs could successfully examine intestinal tumor mice from healthy mice, indicating a potential utility for early diagnosis of intestinal tumors.

Activity Descriptors Derived from Comparison of Mo and Fe as Active Metal for Methane Conversion to Aromatics.

Producing aromatics directly from the smallest hydrocarbon building block, methane, is attractive because it could help satisfy increasing demand for aromatics while filling the gap created by decreased production from naphtha crackers. The system that catalyzes the direct methane dehydroaromatization (MDA) best so far is Mo supported on zeolite. Mo has shown to outperform other transition metals (TMs). Here we attempt to explain the superiority of Mo by directly comparing Fe and Mo supported on HZSM-5 zeolite. To determine the most important parameters responsible for the superior performance of Mo, detailed characterization using X-ray absorption spectroscopy (XAS) techniques combined with catalytic testing and theoretical calculations are performed. The higher abundance of mono- and dimeric sites for the Mo system, their ease of carburization in methane, as well as intrinsically lower activation energy barriers of breaking the methane C-H bond over Mo explain the better catalytic performance. In addition, a pretreatment in CO is presented to more easily carburize Fe and thereby improve its catalytic performance.

Lateral Adsorbate Interactions Inhibit HCOO- while Promoting CO Selectivity for CO2 Electrocatalysis on Silver.

Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO2 ER). Herein, we study the role of the formate (HCOO- ) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton-electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface-enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O-bound bidentate species on polycrystalline Ag during CO2 ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO- and H2 production and a higher selectivity towards CO.

Methane dehydroaromatization catalyzed by Mo/ZSM-5: location-steered activity and mechanism.

This work examined the location-steered catalytic behavior of Mo/ZSM-5 catalyst for one-step methane dehydroaromatization to benzene reaction. The results indicated that α-site is the preferred location for the formation of ethylene, the main intermediate for aromatics production via the propagation pathway, while δ-site is favorable for the hydrocarbon pool aggregation reaction pathway.

Toward the Rational Design of More Efficient Mo2C Catalysts for Hydrodeoxygenation-Mechanism and Descriptor Identification.

Viable alternatives to scarce and expensive noble-metal-based catalysts are transition-metal carbides such as Mo and W carbides. It has been shown that these are active and selective catalysts in the hydrodeoxygenation of renewable lipid-based feedstocks. However, the reaction mechanism and the structure-activity relationship of these transition-metal carbides have not yet been fully clarified. In this work, the reaction mechanism of butyric acid hydrodeoxygenation (HDO) over molybdenum carbide (Mo2C) has been studied comprehensively by means of density functional theory coupled with microkinetic modeling. We identified the rate-determining step to be butanol dissociation: C4H9*OH + * → C4H9* + *OH. Then we further explored the possibility to facilitate this step upon heteroatom doping and found that Zr- and Nb-doped Mo2C are the most promising catalysts with enhanced HDO catalytic activity. Linear-scaling relationships were established between the electronic and geometrical descriptors of the dopants and the catalytic performance of various doped Mo2C catalysts. It was demonstrated that descriptors such as dopants' d-band filling and atomic radius play key roles in governing the catalytic activity. This fundamental understanding delivers practical strategies for the rational design of Mo2C-based transition-metal carbide catalysts with improved HDO performance.

Aromatic Amine-Functionalized Covalent Organic Frameworks (COFs) for CO2/N2 Separation.

CO2 is a prominent example for an exhaust gas, and it is known for its high impact on global warming. Therefore, carbon capture from CO2 emissions of industrial processes is increasingly important to halt and prevent the disruptive consequences of global warming. Covalent organic frameworks (COFs) as porous nanomaterials have been shown to selectively adsorb CO2 in high quantities and with high CO2/N2 selectivity. Interactions with amines are recognized to selectively adsorb CO2 and help capture it from exhaust emissions. Herein, a novel COF (Me3TFB-(NH2)2BD), which was not accessible via a direct condensation reaction, was synthetized by dynamic linker exchange starting with Me3TFB-BD. Despite the linker exchange, the porosity of the COF was largely maintained, resulting in a high BET surface area of 1624 ± 89 m2/g. The CO2 and N2 adsorption isotherms at 273 and 295 K were studied to determine the performance in carbon capture at flue gas conditions. Me3TFB-(NH2)2BD adsorbs 1.12 ± 0.26 and 0.72 ± 0.07 mmol/g of CO2 at 1 bar and 273 and 295 K, respectively. The COF shows a high CO2/N2 IAST selectivity under flue gas conditions (273 K:83 ± 11, 295 K: 47 ± 11). The interaction of the aromatic amine groups with CO2 is based on physisorption, which is expected to make the regeneration of the material energy efficient.

Enantiospecific Synthesis of Aniline-Derived Sulfonimidamides.

Reaction of sulfonimidoyl fluorides with anilines and Ca(NTf2)2 results in the formation of chiral sulfonimidamides. The reaction proceeds with inversion of the stereocenter at a sulfur atom. Enantiospecificity of the reaction was observed for all studied non-heterocyclic anilines. Combined experimental and computational mechanistic studies highlight chelate-type coordination of the sulfonimidoyl group to Ca(NTf2)2 and the formation of a SN2-like transition state, in which leaving F- coordinates with the Ca2+ ion.

A thorough investigation of the active titanium species in TS-1 zeolite by in situ UV resonance raman spectroscopy.

A thorough investigation of the active titanium species in TS-1 zeolite was conducted by in situ UV resonance Raman spectroscopy combined with UV/Vis diffuse reflectance spectroscopy, DFT calculations, and epoxidation experiments. A new titanium species was identified with a characteristic Raman band at 695 cm(-1) when excited at the 266 nm laser line. It is shown that the newly found titanium species is active in the epoxidation reactions in addition to the tetrahedrally coordinated titanium species. However, the acidity of the new titanium species could catalyze the ring-opening reactions of the epoxy products. It results in a lower selectivity toward the epoxy products relative to that of the tetrahedrally coordinated titanium species. The side reaction can be suppressed by the addition of a weak basic reagent.