From Supramolecular Species to Self‐Templated Porous Carbon and Metal‐Doped Carbon for Oxygen Reduction Reaction Catalysts

The preparation of carbon materials usually involves the decomposition of precursors and the reorganization of the as‐generated fragments. However, the cleavage of bonds and the simultaneous formation of new bonds at nearly the same positions prevents effective yet precise fabrication. Herein, a supramolecular precursor, cucurbit[6]uril, that contains multiple bonds with distinct bond strengths is proposed to decouple the twin problem of simultaneous bond cleavage and formation, allowing multistage transformations to hierarchical porous carbon and metal‐doped carbon in a single yet effective pyrolysis step without the need of a template or additional purification. As a proof‐of‐concept, the Fe‐doped carbon electrocatalysts realized a Pt/C‐like half‐wave potential of 0.869 V vs. RHE and small Tafel slope of 51.3 mV dec^?1 in oxygen reduction reaction.     

Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts

The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO₂ utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO₂ catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.     

Asymmetric Allylic Alkylation with Deconjugated Carbonyl Compounds: Direct Vinylogous Umpolung Strategy

An atom‐economic and highly efficient vinylogous umpolung strategy is developed for deconjugated carbonyl compounds, which generate electron‐deficient π‐allylpalladium complexes with Pd(OAc)₂ under ligand‐free conditions. In cooperation with a chiral‐phosphonium‐based phase‐transfer catalyst, the asymmetric direct oxidative allylic alkylations of 3‐substituted oxindoles are furnished under O₂ atmosphere. The γ‐ or even remote ?‐regioselective alkylation products, with substantial substituents, are delivered with excellent enantioselectivity, and can be further used to access diverse chiral spirocyclic architectures effectively. The Mukaiyama dienol silyl ether can be utilized similarly, indicating that the current active π‐allylpalladium species results from tautomerization of the Pd^II‐dienolate intermediate.     

Metal‐Free Oxidative B−N Coupling of nido‐Carborane with N‐Heterocycles

A general method for the oxidative substitution of nido‐carborane (7,8‐C₂B₉H₁₂^?) with N‐heterocycles has been developed by using 2,3‐dichloro‐5,6‐dicyanobenzoquinone (DDQ) as an oxidant. This metal‐free B?N coupling strategy, in both inter‐ and intramolecular fashions, gave rise to a wide array of charge‐compensated, boron‐substituted nido‐carboranes in high yields (up to 97 %) with excellent functional‐group tolerance under mild reaction conditions. The reaction mechanism was investigated by density‐functional theory (DFT) calculations. A successive single‐electron transfer (SET), B?H hydrogen‐atom transfer (HAT), and nucleophilic attack pathway is proposed. This method provides a new approach to nitrogen‐containing carboranes with potential applications in medicine and materials.     

Suppressed Mobility of Negative Charges in Polymer Electrolytes with an Ether‐Functionalized Anion

Suppressing the mobility of anionic species in polymer electrolytes (PEs) is essential for mitigating the concentration gradient and internal cell polarization, and thereby improving the stability and cycle life of rechargeable alkali metal batteries. Now, an ether‐functionalized anion (EFA) is used as a counter‐charge in a lithium salt. As the salt component in PEs, it achieves low anionic diffusivity but sufficient Li‐ion conductivity. The ethylene oxide unit in EFA endows nanosized self‐agglomeration of anions and trapping interactions between the anions and its structurally homologous matrix, poly(ethylene oxide), thus suppressing the mobility of negative charges. In contrast to previous strategies of using anion traps or tethering anions to a polymer/inorganic backbone, this work offers a facile and elegant methodology on accessing selective and efficient Li‐ion transport in PEs and related electrolyte materials (for example, composites and hybrid electrolytes).     

Fluorographdiyne: A Metal‐Free Catalyst for Applications in Water Reduction and Oxidation

A highly efficient bifunctional metal‐free catalyst was prepared by growth of three‐dimensional porous fluorographdiyne networks on carbon cloth (p‐FGDY/CC). Our experiments and density functional theory (DFT) calculations show the 3D p‐FGDY/CC network is highly active and it is a high potential metal‐free catalyst for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), as well as overall water splitting (OWS) under both acidic and alkaline conditions. The experimental and theoretical results show very good consistency; for example, in the HER process, p‐FGDY/CC exhibits small overpotentials of 82 and 92 mV to achieve 10 mA cm^?2 under alkaline and acidic conditions, respectively. This ensures an even higher selectivity for the adsorption/desorption of various O/H intermediate species. The essential key promotion accomplishes a bifunctional H₂O redox performance application under pH‐universal electrochemical conditions.     

Switching on the Photocatalysis of Metal–Organic Frameworks by Engineering Structural Defects

Defect engineering is a versatile approach to modulate band and electronic structures as well as materials performance. Herein, metal–organic frameworks (MOFs) featuring controlled structural defects, namely UiO‐66‐NH₂‐X (X represents the molar equivalents of the modulator, acetic acid, with respect to the linker in synthesis), were synthesized to systematically investigate the effect of structural defects on photocatalytic properties. Remarkably, structural defects in MOFs are able to switch on the photocatalysis. The photocatalytic H₂ production rate presents a volcano‐type trend with increasing structural defects, where Pt@UiO‐66‐NH₂‐100 exhibits the highest activity. Ultrafast transient absorption spectroscopy unveils that UiO‐66‐NH₂‐100 with moderate structural defects possesses the fastest relaxation kinetics and the highest charge separation efficiency, while excessive defects retard the relaxation and reduce charge separation efficiency.     

In Situ Observation of Dynamic Galvanic Replacement Reactions in Twinned Metallic Nanowires by Liquid Cell Transmission Electron Microscopy

Galvanic replacement is a versatile approach to prepare hollow nanostructures with controllable morphology and elemental composition. The primary issue is to identify its fundamental mechanism. In this study, in situ liquid cell transmission electron microscopy was employed to monitor the dynamic reaction process and to explore the mechanism of galvanic replacement. The detailed reaction process was revealed based on in situ experiments in which small Au particles first appeared around Ag nanowires; they coalesced, grew, and adhered to Ag nanowires. After that, small pits grew from the edge of Ag nanowires to form tubular structures, and then extended along the Ag nanowires to obtain hollowed structures. All of our experimental observations from the viewpoint of electron microscopy, combined with DFT calculations, contribute towards an in‐depth understanding of the galvanic replacement reaction process and the design of new materials with hollow structures.     

酸洗脱灰处理对新疆和丰低阶煤结构和萃取性能的影响

对新疆和丰低阶煤样进行酸洗脱灰处理,通过相关表征,分析了脱灰处理对煤样主体结构、石油醚和CS₂萃取性能的影响。FT-IR表征表明,煤样经酸洗脱灰处理,结构仅发生了微弱改变,酸洗煤样（AC）仅在1712 cm^-1处出现了较弱的原煤样（RC）所没有的羧酸类C=O吸收峰。由TG-DTG表征可知,酸洗使得煤中小分子键断裂,但并未破坏煤样的大分子网络主体结构。以石油醚（PE）和CS₂为溶剂对RC和AC两煤样进行常温两级超声萃取的研究表明,AC煤样的PE和CS₂萃取率均高于RC煤样,分别从0.16%和0.53%（RC煤样）增加到0.17%和0.64%,且萃取速率也更大,显著降低了煤样的溶剂萃取次数。萃取物的FT-IR和GC-MS分析表明,酸洗处理不仅能有效脱除煤样中的杂原子,且使得煤样CS₂萃取物的种类增加。另外,由萃余物TG-DTG结果可知,超声萃取主要是一个物理溶胀过程,并没有破坏煤样的大分子主体结构。