Optimal Oxophilicity at the Fe-Nx Interface Enhances the Generation of Singlet Oxygen for Efficient Fenton-Like Catalysis.

In the pursuit of efficient singlet oxygen generation in Fenton-like catalysis, the utilization of single-atom catalysts (SACs) emerges as a highly desired strategy. Here, a discovery is reported that the single-atom Fe coordinated with five N-atoms on N-doped porous carbon, denoted as Fe-N5/NC, outperform its counterparts, those coordinated with four (Fe-N4/NC) or six N-atoms (Fe-N6/NC), as well as state-of-the-art SACs comprising other transition metals. Thus, Fe-N5/NC exhibits exceptional efficacy in activating peroxymonosulfate for the degradation of organic pollutants. The coordination number of N-atoms can be readily adjusted by pyrolysis of pre-assembly structures consisting of Fe3+ and various isomers of phenylenediamine. Fe-N5/NC displayed outstanding tolerance to environmental disturbances and minimal iron leaching when incorporated into a membrane reactor. A mechanistic study reveals that the axial ligand N reduces the contribution of Fe-3d orbitals in LUMO and increases the LUMO energy of Fe-N5/NC. This, in turn, reduces the oxophilicity of the Fe center, promoting the reactivity of *OO intermediate-a pivotal step for yielding singlet oxygen and the rate-determining step. These findings unveil the significance of manipulating the oxophilicity of metal atoms in single-atom catalysis and highlight the potential to augment Fenton-like catalysis performance using Fe-SACs.

Polymer Backbone Chemistry Shapes the Alkaline Stability of Metallopolymer Anion-Exchange Membranes.

Anion-exchange membrane fuel cells and water electrolyzers have garnered significant attention in past years due to their potential role in sustainable and affordable energy conversion and storage. However, the chemical stability of the polymeric anion-exchange membranes (AEMs), the key component in these devices, currently limits their lifespan. Recently, metallopolymers have been proposed as chemically stable alternatives to organic cations, using metal centers as ion transporters. In metallopolymer AEMs, various properties such as alkaline stability, water uptake, flexibility, and performance, are determined by both the metal complex and polymer backbone. Herein we present a systematic study investigating the influence of the polymer backbone chemistry on some of these properties, focusing on the alkaline stability of low-oxophilicity gold metallopolymers. Despite the use of a common N-heterocyclic carbene ligand, upon gold metalation using the same reaction conditions, different polymer backbones end up forming different gold complexes. These findings suggest that polymer chemistry affects the metalation reaction in addition to the other properties relevant to AEM performance.

Designing Dual-Site Catalysts for Selectively Converting CO2 into Methanol.

The variability of CO2 hydrogenation reaction demands new potential strategies to regulate the fine structure of the catalysts for optimizing the reaction pathways. Herein, we report a dual-site strategy to boost the catalytic efficiency of CO2-to-methanol conversion. A new descriptor, τ, was initially established for screening the promising candidates with low-temperature activation capability of CO2, and sequentially a high-performance catalyst was fabricated centred with oxophilic Mo single atoms, who was further decorated with Pt nanoparticles. In CO2 hydrogenation, the obtained dual-site catalysts possess a remarkably-improved methanol generation rate (0.27 mmol gcat. -1 h-1). For comparison, the singe-site Mo and Pt-based catalysts can only produce ethanol and formate acid at a relatively low reaction rate (0.11 mmol gcat. -1 h-1 for ethanol and 0.034 mmol gcat. -1 h-1 for formate acid), respectively. Mechanism studies indicate that the introduction of Pt species could create an active hydrogen-rich environment, leading to the alterations of the adsorption configuration and conversion pathways of the *OCH2 intermediates on Mo sites. As a result, the catalytic selectivity was successfully switched.

Alkaline Stability of Low Oxophilicity Metallopolymer Anion-Exchange Membranes.

Anion-exchange membrane fuel cells (AEMFCs) are promising energy conversion devices due to their high efficiency. Nonetheless, AEMFC operation time is currently limited by the low chemical stability of their polymeric anion-exchange membranes. In recent years, metallopolymers, where the metal centers assume the ion transport function, have been proposed as a chemically stable alternative. Here we present a systematic study using a polymer backbone with side-chain N-heterocyclic carbene (NHC) ligands complexed to various metals with low oxophilicity, such as copper, zinc, nickel, and gold. The golden metallopolymer, using the metal with the lowest oxophilicity, demonstrates exceptional alkaline stability, far superior to state-of-the-art quaternary ammonium cations, as well as good in situ AEMFC results. These results demonstrate that judiciously designed metallopolymers may be superior to purely organic membranes and provides a scientific base for further developments in the field.

AuBr3-catalyzed azidation of per-O-acetylated and per-O-benzoylated sugars.

Herein we report, for the first time, the successful anomeric azidation of per-O-acetylated and per-O-benzoylated sugars by catalytic amounts of oxophilic AuBr3 in good to excellent yields. The method is applicable to a wide range of easily accessible per-O-acetylated and per-O-benzoylated sugars. While reaction with per-O-acetylated and per-O-benzoylated monosaccharides was complete within 1-3 h at room temperature, the per-O-benzoylated disaccharides needed 2-3 h of heating at 55 °C.

Amorphous MoOx with High Oxophilicity Interfaced with PtMo Alloy Nanoparticles Boosts Anti-CO Hydrogen Electrocatalysis.

Advancing electrocatalysts for alkaline hydrogen oxidation/evolution reaction (HOR/HER) is essential for anion exchange membrane-based devices. The state-of-the-art Pt-based electrocatalysts for alkaline HOR suffer from low intrinsic activities and severe CO poisoning due to the challenge of simultaneously optimizing surface adsorption toward different adsorbates. Herein, this challenge is overcome by tuning an atomic MoOx layer with high oxophilicity onto PtMo nanoparticles (NPs) with optimized Had , OHad , and COad adsorption for boosting anti-CO-poisoning hydrogen-cycle electrocatalysis in alkaline media. For alkaline HOR, this catalyst exhibits high kinetics and an exchange current density of 3.19 mA µgPt -1 at 50 mV versus reversible hydrogen electrode and 0.83 mA cmPt -2 , 10.3- and 3.8-fold higher than those of commercial Pt/C, respectively. For alkaline HER, it achieves an unprecedented overpotential of 37 mV at 10 mA cm-2 . Experimental and theoretical studies show that the orchestrated electronic and oxophilic regulation of the PtMo/MoOx interface NPs simultaneously optimizes Had and OHad adsorption for boosting alkaline hydrogen electrocatalysis, whereas reactive oxygen from the amorphous MoOx atomic layer lowers the CO oxidation reaction barrier, leading to superior anti-poisoning ability even at 100 ppm CO.

Engineering Surface Oxophilicity of Copper for Electrochemical CO2 Reduction to Ethanol.

Copper-based materials are known for converting CO2 into deep reduction products via electrochemical reduction reaction (CO2 RR). As the major multicarbon products (C2+ ), ethanol (C2 H5 OH) and ethylene (C2 H4 ) are believed to share a common oxygenic intermediate according to theoretical studies, while the key factors that bifurcate C2 H5 OH and C2 H4 pathways on Cu-based catalysts are not fully understood. Here, a surface oxophilicity regulation strategy to enhance C2 H5 OH production in CO2 RR is proposed, demonstrated by a Cu-Sn bimetallic system. Compared with bare Cu catalyst, the Cu-Sn bimetallic catalysts show improved C2 H5 OH but suppressed C2 H4 selectivity. The experimental results and theoretical calculations demonstrate that the surface oxophilicity of Cu-Sn catalysts plays an important role in steering the protonation of the key oxygenic intermediate and guides the reaction pathways to C2 H5 OH. This study provides new insights into the electrocatalyst design for enhanced production of oxygenic products from CO2 RR by engineering the surface oxophilicity of copper-based catalysts.

Unique (100) Surface Configuration Enables Promising Oxygen Reduction Performance for Pt3Co Nanodendrite Catalysts.

Selective exposure of active surfaces of Pt-based electrocatalysts has been demonstrated as an effective strategy to improve Pt utilization and promote oxygen reduction reaction (ORR) activity in fuel cell application. However, challenges remain in stabilizing those active surface structures, which often suffer undesirable degradation and poor durability along with surface passivation, metal dissolution, and agglomeration of Pt-based electrocatalysts. To overcome the aforementioned obstacles, we here demonstrate the unique (100) surface configuration enabling active and stable ORR performance for bimetallic Pt3Co nanodendrite structures. Using elaborate microscopy and spectroscopy characterization, it is revealed that the Co atoms are preferentially segregated and oxidized at the Pt3Co(100) surface. In situ X-ray absorption spectroscopy (XAS) shows that such (100) surface configuration prevents the oxygen chemisorption and oxide formation on active Pt during the ORR process. Thus, the Pt3Co nanodendrite catalyst shows not only a high ORR mass activity of 730 mA/mg at 0.9 V vs RHE, which is 6.6-fold higher than that of the Pt/C, but also impressively high stability with 98% current retention after the acceleration degradation test in acid media for 5000 cycles, far exceeding the Pt or Pt3Co nanoparticles. Density functional theory (DFT) calculation also confirms the lateral and structural effects from the segregated Co and oxides on the Pt3Co(100) surface in reducing the catalyst oxophilicity and the free energy for the formation of an OH intermediate in the ORR.

Catalytic hydrotreatment of kraft lignin into aromatic alcohols over nickel-rhenium supported on niobium oxide catalyst.

Direct hydrogenolysis of Kraft lignin was catalyzed over a series of supported Ni or Re catalysts in ethanol solvent. The best results showed that the oil yield of 96.70 wt% was obtained with less char formation at 330 °C for 3 h over 5Ni-5Re/Nb2O5 catalyst. Product analysis demonstrated that the monomer yield of 35.41 wt% was given under mild condition, and low-molecular-weight aromatic alcohols were the main component in the liquid products. Ethanol was found to be more effective in H2 production and facilitated the transformation of phenolic monomers to aromatic chemicals. The results confirmed that the optimal 5Ni-5Re/Nb2O5 catalyst had superior oxophilicity and appropriate acid sites, which improved the ability to directly remove the methoxyl and hydroxyl groups of lignin-derived phenolic compounds without aromatic ring hydrogenation. In addition, the temperature, time and solvent effects on the lignin depolymerization were also investigated.