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<jats:title>Abstract</jats:title><jats:p>Functional porous coating on zinc electrode is emerging as a powerful ionic sieve to suppress dendrite growth and side reactions, thereby improving highly reversible aqueous zinc ion batteries. However, the ultrafast charge rate is limited by the substantial cation transmission strongly associated with dehydration efficiency. Here, we unveil the entire dynamic process of solvated Zn<jats:sup>2+</jats:sup> ions’ continuous dehydration from electrolyte across the MOF‐electrolyte interface into channels with the aid of molecular simulations, taking zeolitic imidazolate framework ZIF‐7 as proof‐of‐concept. The moderate concentration of 2 M ZnSO<jats:sub>4</jats:sub> electrolyte being advantageous over other concentrations possesses the homogeneous water‐mediated ion pairing distribution, resulting in the lowest dehydration energy, which elucidates the molecular mechanism underlying such concentration adopted by numerous experimental studies. Furthermore, we show that modifying linkers on the ZIF‐7 surface with hydrophilic groups such as −OH or −NH<jats:sub>2</jats:sub> can weaken the solvation shell of Zn<jats:sup>2+</jats:sup> ions to lower the dehydration free energy by approximately 1 eV, and may improve the electrical conductivity of MOF. These results shed light on the ions delivery mechanism and pave way to achieve long‐term stable zinc anodes at high capacities through atomic‐scale modification of functional porous materials.</jats:p>

<jats:p>Lithium and sodium metal batteries continue to occupy the forefront of battery research. Their exceptionally high energy density and nominal voltages are highly attractive for cutting‐edge energy storage applications. Anode‐free metal batteries are also coming into the research spotlight offering improved safety and even higher energy densities than conventional metal batteries. However, uneven metal nucleation and growth which leads to dendrites continues to limit the commercialisation of conventional and anode‐free metal batteries alike. This review connects models and theories from well‐established fields in metallurgy and electrodeposition to both conventional and anode‐free metal batteries. These highly applicable models and theories explain the driving forces of uneven metal growth and can inform future experiment design. Finally, the models and theories that are most relevant to each anode‐related cell component are identified. Keeping these specific models and theories in mind will assist with rational design for these components.</jats:p>

<jats:p>Biomass photoreforming is a promising method to provide both a clean energy resource in the form of hydrogen (H2) and valuable chemicals as the results of water reduction and biomass oxidation. To overcome the poor contact between heterogeneous photocatalysts and biomass substrates, we fabricated a new photoredox cascade catalyst by combining a homogeneous catalyst, 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO), and a heterogeneous dual‐dye sensitized photocatalyst (DDSP) composed of two Ru(II)‐polypyridine photosensitizers (RuP6 and RuCP6) and Pt‐loaded TiO2 nanoparticles. During blue‐light irradiation (λ = 460 ± 15 nm; 80 mW), the DDSP photocatalytically reduced aqueous protons to form H2 and simultaneously oxidized TEMPO· radicals to generate catalytically active TEMPO+. It oxidized biomass substrates (water‐soluble glycerol and insoluble cellulose) to regenerate TEMPO·. In the presence of N‐methyl imidazole as a proton transfer mediator, the photocatalytic H2 production activities for glycerol and cellulose reforming reached 2670 and 1590 µmol H2 (gTiO2)‐1 h‐1, respectively, which were comparable to those of state‐of‐the‐art heterogeneous photocatalysts.</jats:p>

<jats:title>Abstract</jats:title><jats:p>Electron‐deficient acridones and in situ generated acridinium salts are reported as potent, closed‐shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open‐shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed‐shell, neutral, diffusion‐controlled photocatalysis. Brønsted acid activation of acridones dramatically increases excited state oxidation power (by +0.8 V). Upon reduction of protonated acridones, they transform to electron‐deficient acridinium salts as even more potent photooxidants (*<jats:italic>E</jats:italic><jats:sub>1/2</jats:sub>=+2.56–3.05 V vs SCE). These oxidize even electron‐deficient arenes where conventional acridinium salt photooxidants have thusfar been limited to electron‐rich arenes. Surprisingly, upon photoexcitation these electron‐deficient acridinium salts appear to undergo <jats:italic>two electron reductive quenching</jats:italic> to form acridinide anions, spectroscopically‐detected as their protonated forms. This new behaviour is partly enabled by a catalyst preassembly with the arene, and contrasts to conventional SET reductive quenching of acridinium salts. Critically, this study illustrates how redox active chromophoric molecules initially considered photocatalysts can transform during the reaction to catalytically active species with completely different redox and spectroscopic properties.</jats:p>

<jats:title>Abstract</jats:title><jats:p>Herein we report the first example of a supramolecular cage that works as a catalytic molecular reactor to perform transformations over fullerenes in aqueous medium. Taking advantage of the ability of metallo–organic Pd(II)‐subphthalocyanine (SubPc) capsules to form stable host:guest complexes with C<jats:sub>60</jats:sub>, we have prepared a water‐soluble cage that provides a hydrophobic environment for conducting cycloadditions over encapsulated C<jats:sub>60</jats:sub>, namely, Diels–Alder reactions with anthracene. Indeed, the presence of catalytic amounts of SubPc cage dissolved in water promotes co‐encapsulation of insoluble C<jats:sub>60</jats:sub> and anthracene substrates, allowing the reaction to occur inside the cavity under mild conditions. The lower stability of the host:guest complex with the resulting C<jats:sub>60</jats:sub> cycloadduct facilitates its displacement by pristine C<jats:sub>60</jats:sub>, which grants catalytic turnover. Moreover, bis‐addition compounds are regioselectively formed inside the cage when using excess anthracene.</jats:p>

<jats:title>Abstract</jats:title><jats:p>DNA nanotubes (NTs) have attracted extensive interest as artificial cytoskeletons for biomedical, synthetic biology, and materials applications. Here, we report the modular design and assembly of a minimalist yet robust DNA wireframe nanotube with tunable cross‐sectional geometry, cavity size, chirality, and length, while using only four DNA strands. We introduce an h‐motif structure incorporating double‐crossover (DX) tile‐like DNA edges to achieve structural rigidity and provide efficient self‐assembly of h‐motif‐based DNA nanotube (<jats:bold>H‐NT</jats:bold>) units, thus producing programmable, micrometer‐long nanotubes. We demonstrate control of the <jats:bold>H‐NT</jats:bold> nanotube length via short DNA modulators. Finally, we use an enzyme, RNase H, to take these structures out of equilibrium and trigger nanotube assembly at a physiologically relevant temperature, underlining future cellular applications. The minimalist <jats:bold>H‐NTs</jats:bold> can assemble at near‐physiological salt conditions and will serve as an easily synthesized, DNA‐economical modular template for biosensors, plasmonics, or other functional materials and as cost‐efficient drug‐delivery vehicles for biomedical applications.</jats:p>

<jats:p>Solution‐processed quantum dot (QD) based blue emitters are of paramount importance in the field of optoelectronics. Despite large research efforts, examples of efficient deep blue/near UV‐emitting QDs remain rare due to lack of luminescent wide bandgap materials and high defect densities in the existing ones. Here, we introduce a novel type of QDs based on heavy metal free gallium sulfide (Ga2S3) nanocrystals and their core/shell heterostructures Ga2S3/ZnS as well as Ga2S3‐ZnS‐Al2O3. The PL properties of core Ga2S3 QDs exhibit various decay pathways due to intrinsic defects, resulting in a broad overall PL spectrum. We show that the overgrowth of the Ga2S3 core QDs with a ZnS shell results in the suppression of the intrinsic defect mediated states leading to efficient narrow deep blue emission at 400 nm. Passivation of the core/shell structure with amorphous alumina yields a further enhancement of the photoluminescence quantum yield approaching 50% and leads to an excellent optical and colloidal stability. Finally, we develop a strategy for the aqueous phase transfer of the obtained QDs retainining 80% of the initial fluorescence intensity.</jats:p>

<jats:p>The conversion of CO2 into ethanol with renewable H2 has attracted tremendous attention due to its integrated functions of carbon elimination and chemical synthesis, but still being challenging. The electronic property of catalyst is essential to determine the adsorption strength and configuration of the key intermediates, therefore altering the reaction network for targeted synthesis. Here, a carbon buffer layer is employed to tailor the electronic property of the ternary ZnOx‐Fe5C2‐Fe3O4, in which the electron transfer pathway (ZnOx → Fe species or carbon layer) ensures the appropriate adsorption strength of ‐CO* on catalytic interface, facilitating the C‐C coupling between ‐CHx* and ‐CO* for ethanol synthesis. Benefiting from this unique electron transfer buffering effect, extremely high ethanol yield of 366.6 gEtOH kgcat‐1 h‐1 (with CO of 10 vol% co‐feeding) is achieved from CO2 hydrogenation. This work provides a powerful electronic modulation strategy for catalyst design in terms of highly oriented synthesis.</jats:p>

<jats:p>Introducing fluorine (F) groups into a passivator plays an important role in enhancing the defect passivation effect for the perovskite film, which is usually attributed to the direct interaction of F and defect states. However, the interaction between electronegative F and electron‐rich passivation groups in the same molecule, which may influence the passivation effect, is ignored. We herein report that such interactions can vary the electron cloud distribution around the passivation groups and thus changing their coordination with defect sites. By comparing two fluorinated molecules, heptafluorobutylamine (HFBM) and heptafluorobutyric acid (HFBA), we find that the F/–NH2 interaction in HFBM is stronger than the F/–COOH one in HFBA, inducing weaker passivation ability of HFBM than HFBA. Accordingly, HFBA‐based perovskite solar cells (PSCs) provide an efficiency of 24.70% with excellent long‐term stability. Moreover, the efficiency of a large‐area perovskite module (14.0 cm2) based on HFBA reaches 21.13%. Our work offers an insight into understanding an unaware role of the F group in impacting the passivation effect for the perovskite film. ​</jats:p>

<jats:p>Formation of borabicyclo[3.2.0]heptadiene derivatives was achieved via boron‐insertion into aromatic C–C bonds in the photo‐promoted skeletal rearrangement reaction of triarylboranes bearing an ortho‐phosphino substituent (ambiphilic phosphine‐boranes). The borabicyclo[3.2.0]heptadiene derivatives were fully characterized by NMR and X‐ray analyses. These dearomatized products were demonstrated to undergo the reverse reaction in the dark at room temperature, realizing photochemical and thermal interconversion between triarylboranes and boron‐doped bicyclic systems.Experimental and theoretical studies revealed that sequential two electrocyclic reactions involving E/Z‐isomerization of an alkene moiety proceed via a highly strained trans‐borepin intermediate.</jats:p>