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Photocatalytic CO 2 conversion promises an ideal route to store solar energy into chemical bonds. However, sluggish electron kinetics and unfavorable product selectivity remain unresolved challenges. Here, an ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate, and borate-anchored Co single atoms were separately loaded on ultrathin g-C 3 N 4 nanosheets. The optimized nanocomposite photocatalyst produces CO and CH 4 from CO 2 and water under UV–vis light irradiation, exhibiting a 42-fold photoactivity enhancement compared with g-C 3 N 4 and nearly 100% selectivity towards CO 2 reduction. Experimental and theoretical results reveal that the ionic liquid extracts electrons and facilitates CO 2 reduction, whereas Co single atoms trap holes and catalyze water oxidation. More importantly, the maximum electron transfer efficiency for CO 2 photoreduction, as measured with in-situ μs-transient absorption spectroscopy, is found to be 35.3%, owing to the combined effect of the ionic liquid and Co single atoms. This work offers a feasible strategy for efficiently converting CO 2 to valuable chemicals. There is growing interest in designing photocatalysts for CO 2 conversion. Here, the authors combine an ionic liquid with Co single atoms as dual-cocatalysts for g-C 3 N 4 , accelerating electron kinetics and improving CO 2 reduction selectivity.

Metal-organic frameworks that feature hybrid fluorescence and phosphorescence offer unique advantages in white-emitting communities based on their multiple emission centers and high exciton utilization. However, it poses a substantial challenge to realize superior white-light emission in single-component metal-organic frameworks without encapsulating varying chromophores or integrating multiple phosphor subunits. Here, we achieve a high-performance white-light emission with photoluminescence quantum yield of 81.3% via boosting triplet excitons distribution through pressure treatment in single-component Zn-IPA metal-organic frameworks. A novel metal-ligand asymmetrical chelate coordination is successfully integrated into the Zn-IPA after a high-pressure treatment over ~20.0 GPa. This modification unexpectedly endows the targeted sample with a new emergent electronic state to narrow the singlet-triplet energy gap, which effectively accelerates the spin-flipping process for boosted triplet excitons population. Time delay phosphor-converted light-emitting diodes are fabricated with long emission time up to ~7 s after switching off, providing significant advancements for white-light and time-delay lighting applications. Pressure-treatment can alter the optical properties of metal-organic frameworks. Here the authors induce amorphization in Zn-IPA that remains after decompression and enables efficient white-light emission through narrowing the singlet-triplet gap.

Single-component multi-emissive materials with stimuli-responsive properties offer unique advantages in the field of multicolor-tunable photoluminescence (PL). However, precisely modulating the emission of each component and achieving high-efficiency emission present a formidable challenge. Herein, we demonstrate that space-confined charge transfer (CT) turns on bright blue-green-white emission in initially faintly emissive metal-organic frameworks (MOFs) at ambient conditions through pressure treatments. Pressure treatments induce a transition from the initial long-range CT to a space-confined mode, significantly amplifying radiative transitions. Furthermore, the space-confined CT, which occurs between mutually perpendicular ligands, significantly influences the spin-orbit charge transfer intersystem crossing. Precise tuning of space-confined CT kinetics via multi-level pressure treatments allows us to modulate the fluorescence-to-phosphorescence ratio, achieving multicolor-tunable emission in the target MOFs. Our work advances the development of multicolor-tunable smart PL materials and unlocks the potential for their application in atmospheric environments. Stimuli-responsive single-component multi-emissive materials offer unique advantages in photoluminescence. Single-component multi-emissive materials with stimuli-responsive properties offer unique advantages in the field of multicolor-tunable photoluminescence.

CYP 3A4 and CYP 3A5 are two important members of the human cytochrome P450 family. Although their overall structures are similar, the local structures of the active site are different, which directly leads to obvious individual differences in drug metabolic efficacy and toxicity. In this work, midazolam (MDZ) was selected as the probe substrate, and its interaction with two proteins, CYP 3A4 and CYP 3A5, was studied by molecular dynamics simulation (MD) along with the calculation of the binding free energy. The results show that two protein–substrate complexes have some similarities in enzyme–substrate binding; that is, in both complexes, Ser119 forms a high occupancy hydrogen bond with MDZ, which plays a key role in the stability of the interaction between MDZ and the enzymes. However, the complex formed by CYP 3A4 and MDZ is more stable, which may be attributed to the sandwich structure formed by the fluorophenyl group of the substrate with Leu216 and Leu482. Our study interprets the binding differences between two isoform–substrate complexes and reveals a structure–function relationship from the atomic perspective, which is expected to provide a theoretical basis for accurately measuring the effectiveness and toxicity of drugs for individuals in the era of precision medicine.

Solar‐driven CO2 conversion holds great promise in carbon recycling. CO2 activation and hydrogen spillover are crucial for high‐selectivity CO2 reduction, while with great challenges. Here, heteronuclear metal phthalocyanine aggregates with atomically active sites are synthesized and then assembled on BiVO4 nanosheets. The CuNiPc/BiVO4 nanocomposite achieves a 238 mmol gCu−1 h−1 CO yield with nearly 100% selectivity (vs 77% for mononuclear CuPc/BiVO4) without H2 evolution, ranking among top atomic‐engineered photocatalysts. Femtosecond‐transient absorption spectra, in situ synchrotron radiation measurements, and theoretical simulations, etc., reveal that such a difference is mainly ascribed to the fast interfacial Z‐scheme charge transfer kinetics and the synergy catalysis between dual sites in CuNiPc. The Cu–N4 moiety enhances CO2 adsorption and activation relative to CuPc due to the regulated Cu configuration caused by the Ni atom incorporation, while the adjacent Ni–N4 unit activates H2O to generate *H, which subsequently undergoes intramolecular spillover to *Cu–COO site, consequently accessing both CO2 activation and protonation for *COOH generation towards highly selective CO2 reduction. The CuNiPc/BiVO4 heterojunction is designed and synthesized for selective CO2 photoreduction. The cascade interfacial Z‐scheme charge transfer and the intramolecular synergy of Cu–Ni dual sites on CO2 activation and H spillover contribute to the high photocatalytic performance and selectivity.

As a four-electron transfer reaction, oxygen evolution reaction (OER) is limited by large overpotential and slow kinetics. Here, we in-situ synthesized two-dimensional (2D) Ni-Fe metal-organic framework nanosheets on nickel foam (Ni x Fe-TPA/NF, TPA = terephthalic acid) for oxygen evolution in alkaline and alkaline seawater electrolytes. In 1 M KOH, Ni 3 Fe-TPA/NF shows a low overpotential ( η 10 ) of 189 mV at 10 mA·cm −2 and an ultra-low overpotential of only 260 mV at 500 mA·cm −2 . In alkaline seawater, Ni 3 Fe-TPA/NF still provides impressive OER performance, with an η 10 of 265 mV. In-situ Raman characterization results show that the phase transition occurs during the OER, and Ni 3 FeOOH with more oxygen vacancies is in-situ formed, reducing the OER energy barrier. Density functional theory (DFT) reveals that the synergy between Ni and Fe reduces the energy barrier and accelerates the rate-determining step. In addition, the ultra-thin 2D sheet structure and the close combination of Ni 3 FeOOH and highly conductive NF support ensure the high catalytic OER activity. Therefore, the surface reconstruction and structural modification strategy can be used to design and prepare high-performance OER electrocatalysts for energy-related applications.

A variety of heteroleptic ruthenium sensitizers have been engineered and synthesized because of their higher light-harvesting efficiency and lower charge-recombination possibility than the well known homoleptic N3 dye. As such, a great deal of atten- tion has been focused on sensitizers with the general formula Ru（ancillary-ligand）（anchoring-ligand）（NCS）2, among which important examples are Ru（4,4＇-bis（5-hexylthiophen-2-yl）-2,2＇-bipyridine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （C101） and Ru（N-（4-butoxyphenyl）-N-2-pyridinyl-2-pyridinamine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （J13）. In order to simulate experimental conditions with different pH values, the photosensitizing processes of these sensitizers pos- sessing different degrees of deprotonation （2I-I, lit to OH） have been explored theoretically in this work. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of all the complexes in acetonitrile solution are also predicted at the TDDFT （B3LYP） level. The calculated results show that the ancillary ligand contributes to the molecular or- bital （MO） energy levels and absorption transitions. It is intriguing to observe that the introduction of a thiophene group into the ancillary ligand leads directly to the increased energy of the absorption transitions in the 380-450 nm region. The calcula- tions reveal that although deprotonation destabilizes the overall frontier MOs of the chromophores, it tends to exert a greater influence on the unoccupied orbitals than on the occupied orbitals. Consequently, an obvious blue shift was observed for the absorptions and emissions in going from 21-1, 1H to OH. Finally, the optimal degree of deprotonation for C101 and J13 has al- so been evaluated, which is expected to lead to further improvements in the performance of dye-sensitized solar cells （DSSCs） coated with such sensitizers.

Direct non-oxidative dehydrogenation of alkanes produces useful carbon feedstocks and hydrogen fuel. However, breaking the C–H bonds in alkanes typically requires high temperature, stoichiometric oxidants or high-energy ultraviolet light; processes that operate under milder conditions are attractive but tend to have poor efficiency. Here we report Pt/black TiO 2 photocatalysts in which Pt species are close to each other but not directly bonded, exhibiting high performance for alkane dehydrogenation in visible to near-infrared light at room temperature. For cyclohexane dehydrogenation, the turnover number for H 2 production exceeded 100,000 without any deactivation over 80 reaction cycles, far beyond thermal reactions. For methane, 8.2% conversion was achieved with 65% selectivity to propane, rather than the more common ethane. We propose that methane undergoes intramolecular dehydrogenation to produce a methylene intermediate. For C2+ alkanes, fast dehydrogenation (up to 1,440 µmol g −1  h −1 ) to the corresponding olefins was realized. Distinct from isolated Pt + monomers, the collections of Pt + monomers give better photocatalytic activity and selectivity. Dehydrogenation of alkanes produces hydrogen and useful carbon molecules but typically requires harsh conditions to operate effectively. Here the authors show that Pt/TiO 2 photocatalysts where Pt atoms are isolated from, yet still close to, one another are promising for visible-light-driven alkane dehydrogenation.

Electrochemical carbon dioxide reduction reaction (CO 2 RR) powered by renewable electricity offers an attractive approach to reduce carbon emission and at the same time produce valuable chemicals/fuels. To design efficient CO 2 reduction electrocatalyst, it is important to understand the structure-activity relationship. Herein, we design a series of single Co atoms electrocatalysts with well-defined active sites electronic structures, which exhibit outstanding CO 2 RR activity with controllable selectivity to CO. Experimental and density functional theory (DFT) calculation studies show that introducing nitro (amino) ligand next to single Co atom catalytic center with electron-withdrawing (electron-donating) capability favors (hinders) CO 2 reduction catalysis. This work provides an in-depth understanding of how functional ligand affects the splitting of transition metal 3d electron orbital, thereby changing the electron transfer from transition metal active site to CO 2 , which is closely related to the Gibbs free energy of the rate-determining step (CO 2 +e − +*→*CO 2 − ).

absorption and phosphorescent mechanism of three Au(III) complexes, Au(2,5-F 2 C 6 H 3 -C∧C∧C)(C≡C-C 6 H 4 N(C 6 H 5 ) 2 [Au25FPh] , Au(3,5-F 2 C 6 H 3 -C∧C∧C)(C≡C-C 6 H 4 N(C 6 H 5 ) 2 [Au35FPh] , and Au(3,5-F 2 C 6 H 3 -C∧C∧C)(C≡C-C 6 H 4 N(1H-indole) 2 [Au35FID] , are calculated and compared using density functional theory (DFT) and time-dependent DFT (TDDFT). The calculated results reveal that enlarging the center C∧C∧C ligand will result in the enhanced LMCT participation. This theoretical contribution allows design of new Au(III) complexes with higher phosphorescence efficiency.