Simultaneous Interface Engineering and Phase Tuning of CeO2-Decorated Catalysts for Boosted Oxygen Evolution Reaction.

Heterogeneous catalysts have attracted extensive attention among various emerging catalysts for their exceptional oxygen evolution reaction (OER) capabilities, outperforming their single-component counterparts. Nonetheless, the synthesis of heterogeneous materials with predictable, precise, and facile control remains a formidable challenge. Herein, a novel strategy involving the decoration of catalysts with CeO2 is introduced to concurrently engineer heterogeneous interfaces and adjust phase composition, thereby enhancing OER performance. Theoretical calculations suggest that the presence of ceria reduces the free energy barrier for the conversion of nitrides into metals. Supporting this, the experimental findings reveal that the incorporation of rare earth oxides enables the controlled phase transition from nitride into metal, with the proportion adjustable by varying the amount of added rare earth. Thanks to the role of CeO2 decoration in promoting the reaction kinetics and fostering the formation of the genuine active phase, the optimized Ni3FeN/Ni3Fe/CeO2-5% nanoparticles heterostructure catalyst exhibits outstanding OER activity, achieving an overpotential of just 249 mV at 10 mA cm-2. This approach offers fresh perspectives for the conception of highly efficient heterogeneous OER catalysts, contributing a strategic avenue for advanced catalytic design in the field of energy conversion.

A Coordination-Derived Cerium-Based Amorphous-Crystalline Heterostructure with High Electrocatalytic Oxygen Evolution Activity.

The rational design of heterogeneous catalysts is crucial for achieving optimal physicochemical properties and high electrochemical activity. However, the development of new amorphous-crystalline heterostructures is significantly more challenging than that of the existing crystalline-crystalline heterostructures. To overcome these issues, a coordination-assisted strategy that can help fabricate an amorphous NiO/crystalline NiCeOx (a-NiO/c-NiCeOx ) heterostructure is reported herein. The coordination geometry of the organic ligands plays a pivotal role in permitting the formation of coordination polymers with high Ni contents. This consequently provides an opportunity for enabling the supersaturation of Ni in the NiCeOx structure during annealing, leading to the endogenous spillover of Ni from the depths of NiCeOx to its surface. The resulting heterostructure, featuring strongly coupled amorphous NiO and crystalline NiCeOx , exhibits harmonious interactions in addition to low overpotentials and high catalytic stability in the oxygen evolution reaction (OER). Theoretical calculations prove that the amorphous-crystalline interfaces facilitate charge transfer, which plays a critical role in regulating the local electron density of the Ni sites, thereby promoting the adsorption of oxygen-based intermediates on the Ni sites and lowering the dissociation-related energy barriers. Overall, this study underscores the potential of coordinating different metal ions at the molecular level to advance amorphous-crystalline heterostructure design.

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead-free Hybrid Metal Halides.

Generating circularly polarized luminescence (CPL) with simultaneous high photoluminescence quantum yield (PLQY) and dissymmetry factor (glum) is difficult due to usually unmatched electric transition dipole moment (µ) and magnetic transition dipole moment (m) of materials. Herein we tackle this issue by playing a "cascade cationic insertion" trick to achieve strong CPL (with PLQY of ~100 %) in lead-free metal halides with high glum values reaching -2.3×10-2 without using any chiral inducers. Achiral solvents of hydrochloric acid (HCl) and N, N-dimethylformamide (DMF) infiltrate the crystal lattice via asymmetric hydrogen bonding, distorting the perovskite structure to induce the "intrinsic" chirality. Surprisingly, additional insertion of Cs+ cation to substitute partial (CH3)2NH2 + transforms the chiral space group to achiral but the crystal maintains chiroptical activity. Further doping of Sb3+ stimulates strong photoluminescence as a result of self-trapped excitons (STEs) formation without disturbing the crystal framework. The chiral perovskites of indium-antimony chlorides embedded on LEDs chips demonstrate promising potential as CPL emitters. Our work presents rare cases of chiroptical activity of highly luminescent perovskites from only achiral building blocks via spontaneous resolution as a result of symmetry breaking.

Structural Decoration of Porphyrin/Phthalocyanine Photovoltaic Materials.

Porphyrin/phthalocyanine compounds with fascinating molecular structures have attracted widespread attention in the field of solar cells in recent years. In this review, we focus on the pivotal role of porphyrin and phthalocyanine compounds in enhancing the efficiency of solar cells. The review seamlessly integrates the intricate molecular structures of porphyrins and phthalocyanines with their proficiency in absorbing visible light and facilitating electron transfer, key processes in converting sunlight into electricity. By delving into the nuances of intramolecular regulation, aggregated states, and surface/interface structure manipulation, it elucidates how various levels of molecular modifications enhance solar cell efficiency through improved charge transfer, stability, and overall performance. This comprehensive exploration provides a detailed understanding of the complex relationship between molecular design and solar cell performance, discussing current advancements and potential future applications of these molecules in solar energy technology.

Porphyrin Supramolecule as Surface Carrier Modulator Imparts Hole Transporter with Enhanced Mobility for Perovskite Photovoltaics.

Modulating the surface charge transport behavior of hole transport materials (HTMs) would be as an potential approach to improve their hole mobility, while yet realized for fabricating efficient photovoltaic devices. Here, an oxygen bridged dimer-based monoamine FeIII porphyrin supramolecule is prepared and doped in HTM film. Theoretical analyses reveal that the polaron distributed on dimer can be coupled with the parallel arranged polarons on adjacent dimers. This polaron coupling at the interface of supramolecule and HTM can resonates with hole flux to increase hole transport efficiency. Mobility tests reveal that the hole mobility of doped HTM film is improved by 8-fold. Doped perovskite device exhibits an increased efficiency from 19.8 % to 23.2 %, and greatly improved stability. This work provides a new strategy to improve the mobility of HTMs by surface carrier modulation, therefore fabricating efficient photovoltaic devices.

A tube-like Pd@coordination polymer with enhanced solar light harvesting for boosting photocatalytic H2 production in a wide pH range and seawater.

Coordination polymers (CPs) have emerged as promising candidates for photocatalytic H2 production owing to their structural tailorability and functional diversity. However, the development of CPs with high energy transfer efficiency for highly efficient photocatalytic H2 production in a wide pH range still faces many challenges. Here we constructed a novel tube-like Pd(ii) coordination polymer with well-distributed Pd nanoparticles (denoted as Pd/Pd(ii)CPs) based on the coordination assembly of rhodamine 6G and Pd(ii) ions and further photo-reduction under visible light irradiation. Both the Br- ion and double solvent play a key role in forming the hollow superstructures. The resulting tube-like Pd/Pd(ii)CPs exhibit high stability in aqueous solution with the pH range from 3 to 14 due to the high Gibbs free energies of protonation and deprotonation, which provides the feasibility of photocatalytic hydrogen generation in a wide pH range. Electromagnetic field calculations showed that the tube-like Pd/Pd(ii)CPs have a good confinement effect on light. Therefore, the H2 evolution rate could reach 112.3 mmol h-1 g-1 at pH 13 under visible light irradiation, which is far superior to those of reported coordination polymer-based photocatalysts. Moreover, such Pd/Pd(ii)CPs could also reach a H2 production rate of 37.8 mmol h-1 g-1 in seawater under visible light with low optical density (40 mW cm-2) close to morning or cloudy sunlight. The above unique characteristics make the Pd/Pd(ii)CPs possess great potential for practical applications.

A General Preparation of Solid Solution-Oxide Heterojunction Photocatalysts through Metal-Organic Framework Transformation Induced Pre-nucleation.

Solid solution-oxide heterostructures combine the advantages of solid solution and heterojunction materials to improve electronic structure and optical properties by metal doping, and enhance charge separation and transfer in semiconductor photocatalysts by creating a built-in electric field. Nevertheless, the effective design and synthesis of these materials remains a significant challenge. Here, we develop a generally applicable strategy that leverages the transformable properties of metal-organic frameworks (MOFs) to prepare solid solution-oxide heterojunctions with controllable structural and chemical compositions. The process consists of three main steps. First, MOFs with different topological structures and metal centers are transformed, accompanied by pre-nucleation of a metal oxide. Second, solid solution is prepared through calcination of the transformed MOFs. Finally, a heterojunction is formed by combining solid solution with another metal oxide group through endogenous overflow. DFT calculations and study on carrier dynamics show that the structure of the material effectively prevents electrons from returning to the bulk phase, exhibiting superior photocatalytic reduction performance of CO2 . This study is expected to promote the controllable synthesis and research of MOF-derived heterojunctions.

Directional Transformation of Heterometallic Oxo Clusters: A New Approach to Prepare Wide-Bandgap Cathode Interlayers for Perovskite Solar Cells.

Typical wide-band gap cathode interlayer materials are difficulty in reducing interface recombination without limiting charge transport in perovskite solar cells (PSCs). Here, a lead-doped titanium-oxo cluster protected by S-containing ligands is introduced at the interface of perovskite and SnO2 . By in situ heating, the cluster is transformed into PbSO4 -PbTi3 O7 heterostructure. The oxygen atoms from sulfate ion in heterostructure connect with iodine from perovskite to boost interfacial electron extraction and reduce charge recombination. While the yielded metallic interface between PbSO4 and PbTi3 O7 promotes the electron transport across the interface. Finally, an efficiency as high as 24.2 % for the modified PSC is obtained. The heterostructure well-stabilize the interface of perovskite and SnO2 , to greatly improve the device stability. This work provides a novel strategy to prepare wide-band gap cathode interlayer by directional transformation of heterometallic oxo clusters.

Molecular Dipole Modulation of Porphyrins to Enhance Photocatalytic Oxidation Activity for Inactivation of Intracellular Bacteria.

The regulation of molecular structures of porphyrin-based photosensitizers is crucial for yielding the effective singlet oxygen as one of the efficient photocatalytic reactive oxidation species. Here, we select methoxy substitution as an electron donor to decorate the porphyrin rings. Introducing a series of metal ions into porphyrin centers further prepares the methoxy-substituted metalloporphyrins (MPs, M = Co, Ni, Cu, Zn), with the hope of modulating their molecular dipole moments and photocatalytic activity. The theoretical calculation analyses show that the metal-free porphyrin center possesses a higher transition dipole and more delocalized orbitals, leading to efficient charge transfer and improved photocatalytic activity. The metalloporphyrin samples are then polymerized by poly(D, l-lactide-co-glycolide) to be applied to in vitro sterilization experiments. As expected, metal-free porphyrin has good antibacterial ability and good biocompatibility. Moreover, the highly effective bacteriostatic metal-free porphyrin achieves satisfactory photodynamic therapeutic outcomes against intracellular pathogens in cancer cells. This work demonstrates that the molecular dipole modulation of porphyrins is critical for their photocatalytic oxidation and antibacterial ability.

Confinement and passivation of perovskite quantum dots in porous natural palygorskite toward an efficient and ultrastable light-harvesting system in water.

Perovskite quantum dots (QDs) are promising as representative candidates to construct next-generation superior artificial light-harvesting systems (ALHSs). However, their high sensitivity to external environments, especially to water, imposes a stringent limitation for their actual implementation. Herein, by interface engineering and encapsulation with natural palygorskite (PAL), a water-resistant light-harvesting CsPbBr3@PAL antenna was prepared. Molecular dynamics simulations further confirm a significant shielding protection of the PAL matrix to CsPbBr3, facilitating exceptional stability of the CsPbBr3@PAL antenna when exposed to air for 10 months, to 150 °C thermal stress, and even to water for more than 30 days, respectively. Furthermore, as a result of in situ encapsulation of the PAL matrix and defect passivation caused by H-bonding and coordination-bonding interaction, the CsPbBr3@PAL antenna in water shows a substantially enhanced photoluminescence quantum yield (36.2%) and longer lifetime. After sequentially assembling Eosin Y and Rose Bengal in the pores of the PAL matrix, RB-ESY-CsPbBr3@PAL with a sequential two-step efficient Förster resonance energy transfer process exhibited extremely enhanced photocatalytic activity toward Friedel-Crafts alkylation reactions in aqueous solution, 2.5-fold higher than that of corresponding ESY/RB. Our work provides a feasible strategy for the exploitation of ultra-stable halide perovskite-based ALHSs in aqueous media for solar-energy conversion.

Chemical Mechanism-Dominated and Reporter-Tunable Surface-Enhanced Raman Scattering via Directional Supramolecular Assembly.

Molecular resonance can be strengthened by charge transfer, profiting chemical mechanism (CM)-related surface-enhanced Raman scattering (SERS). Herein a supramolecular assembly enabled SERS system is established by functionalizing para-sulfonatocalix[4]arene (pSC4) onto Au3Cu nanocrystals (NCs). Due to the cooperation of Au and Cu, pSC4 is directionally assembled on the surface of Au3Cu NCs via van der Waals force, enabling photoinduced and hydrogen bond-induced charge transfer, which remarkably enhances the Raman scattering of methylene blue (MB) captured by pSC4. In particular, for the C-N and C-C stretching of MB, the contributions of resonance Raman scattering increase up to 80%. In addition, the SERS system is able to display affinities of different host-guest interactions, and further employed to evaluate effects of drugs for Alzheimer's disease. In this work, charge transfer is realized by performing supramolecular assembly on the surface of plasmonic nanomaterials, providing an avenue to design CM-related and reporter-tunable SERS systems.

Homogeneously Large Polarons in Aromatic Passivators Improves Charge Transport between Perovskite Grains for >24 % Efficiency in Photovoltaics.

Aromatic passivators, such as porphyrin, with large π-backbones have attracted considerable attention to boost the charge carrier in polycrystalline perovskite films, thus enabling the fabrication of efficient and stable perovskite solar cells (PSCs). However, they often self-assemble into supramolecules that probably influence the charge-transfer process in the perovskite grain boundary. Here, by doping a monoamine Cu porphyrin into perovskite films, two porphyrin-based self-assembled supramolecules were successfully prepared between perovskite grains. Crystal structures and theoretical analyses reveal the presence of a stronger interaction between the amine units and the central Cu ions of neighbouring porphyrins in one of the supramolecules. This has a modified effect on the dipole direction of the porphyrins to be quantized as homogeneously large polarons (HLPs) in a periodic lattice. The porphyrin supramolecules can stabilize perovskite grain boundaries to greatly improve the stability of PSCs, while the HLPs-featured supramolecule facilitates hole transport across perovskite grains to remarkably increase the cell performance to as high as 24.2 %. This work proves that the modulation of the intermolecular interaction of aromatic passivators to yield HLPs is crucial for the cascaded acceleration of charge transport between perovskite grains.

Grain Boundary Engineering with Self-Assembled Porphyrin Supramolecules for Highly Efficient Large-Area Perovskite Photovoltaics.

Grain boundary management is critical to the performance and stability of polycrystalline perovskite solar cells (PSCs), especially large-area devices. However, typical passivators are insulating in nature and limit carrier transport. Here, we design a supramolecular binder for grain boundaries to simultaneously passivate defects and promote hole transport across perovskite grain boundaries. By doping the monoamine porphyrins (MPs, M = Co, Ni, Cu, Zn, or H) into perovskite films, MPs self-assemble into supramolecules at grain boundaries. Organic cations in perovskites protonate MPs in supramolecules to form ammonium porphyrins bound on the perovskite grain surface, to passivate defects and extract holes from the perovskite lattice. Periodic polarons in supramolecules (especially NiP-supramolecule) promote the transport of extracted holes across boundaries, reducing nonradiative carrier recombination. The NiP-doped PSCs reveal a certified efficiency of 22.1% for an active area of 1.0 cm2 with the remarkably improved open-circuit voltage and fill factor. The unencapsulated device retained over 80% initial performance under AM 1.5G solar light continuous illumination or heating at 85 °C over 3000 h.

Azo-Enhanced Raman Scattering for Enhancing the Sensitivity and Tuning the Frequency of Molecular Vibrations.

Raman scattering provides stable narrow-banded signals that potentially allow for multicolor microscopic imaging. The major obstacle for the applications of Raman spectroscopy and microscopy is the small cross section of Raman scattering that results in low sensitivity. Here, we report a new concept of azo-enhanced Raman scattering (AERS) by designing the intrinsic molecular structures using resonance Raman and concomitant fluorescence quenching strategies. Based on the selection of vibrational modes and the enhancing unit of azobenzenes, we obtained a library of AERS molecules with specific Raman signals in the fingerprint and silent frequency regions. The spectral characterization and molecular simulation revealed that the azobenzene unit conjugated to the vibrational modes significantly enhanced Raman signals due to the mechanism of extending the conjugation system, coupling the electronic-vibrational transitions, and improving the symmetry of vibrational modes. The nonradiative decay of azobenzene from the excited state quenched the commitment fluorescence, thus providing a clean background for identifying Raman scattering. The most sensitive AERS molecules produced Raman signals of more than 4 orders of magnitude compared to 5-ethynyl-2'-deoxyuridine (EdU). In addition, a frequency tunability of 10 distinct Raman bands was achieved by selecting different types of vibrational modes. This methodology of AERS allows for designing small-molecule Raman probes to visualize various entities in complex systems by multicolor spontaneous Raman imaging. It will open new prospects to explore innovative applications of AERS in interdisciplinary research fields.

Red-light-responsive coordination polymers nanorods: New strategy for ultrasensitive photothermal detection of targeted cancer cells.

The development of highly sensitive and simple detection methods for cancer cells is an important challenge to achieve early cancer diagnosis and effective treatment. In this paper, folic acid (FA)-conjugated platinum (IV) methylene blue (MB) coordination polymers nanorods (denoted as FA-PtCPs NRs) were developed by the photochemical method. The structure of the PtCPs NRs was investigated using the meta-dynamics and genetic algorithms (MTD-GC) method, and it was found that the coordination bond was formed between platinum (IV) and N atoms of MB. The field emission scanning electron microscope (FE-SEM) and transmission electron microscope (TEM) indicated that the morphology of PtCPs NRs was rod-like. The resulting FA-PtCPs NRs was used for the specific and ultra-sensitive temperature detection of cancer cells based on PtCPs NRs as a signal trigger unit and FA as a target recognition tool. After three-step reaction, oxidized 3,3',5,5'-tetramethylbenzidine (ox-TMB) with photothermal effect was obtained. Under 660 nm laser irradiation, such detection platform can convert the molecular recognition signal between FA and folate receptor (FR) of cancer cells into readable temperature value, which can be directly read by an ordinary thermometer, with a detection limit as low as 2 cells/mL. In addition, FA-PtCPs NRs could be used as fluorescent probes for in-situ bioimaging. Therefore, this photothermal sensing platform has a broad prospect in the field of point-of-care detection of cancer cells.

Intramolecular Electric Field Construction in Metal Phthalocyanine as Dopant-Free Hole Transporting Material for Stable Perovskite Solar Cells with >21 % Efficiency.

Low conductivity and hole mobility in the pristine metal phthalocyanines greatly limit their application in perovskite solar cells (PSCs) as the hole-transporting materials (HTMs). Here, we prepare a Ni phthalocyanine (NiPc) decorated by four methoxyethoxy units as HTMs. In NiPc, the two oxygen atoms in peripheral substituent have a modified effect on the dipole direction, while the central Ni atom contributes more electron to phthalocyanine ring, thus efficiently increasing the intramolecular dipole. Calculation analyses reveal the extracted holes within NiPc are mainly concentrated on the phthalocyanine core induced by the intramolecular electric field, and further to be transferred by π-π stacking space channel between NiPc molecules. Finally, the best efficiency of PSCs with NiPc as dopant-free HTMs realizes a record value of 21.23 % (certified 21.03 %). The PSCs also exhibit the good moisture, heating and light stabilities. This work provides a novel way to improve the performance of PSCs with free-doped metal phthalocyanines as HTMs.

Chiral surface plasmon-enhanced chiral spectroscopy: principles and applications.

In this review, the development context and scientific research results of chiral surface plasmons (SPs) in recent years are classified and described in detail. First, the principle of chiral SPs is introduced through classical and quantum theory. Following this, the classification and properties of different chiral structures, as well as the superchiral near-field, are introduced in detail. Second, we describe the excitation and propagation properties of chiral SPs, which lays a good foundation for the application of chiral SPs and their chiral spectra in various fields. After that, we have summarized the recent research results of chiral SPs and their applications in the areas of biology, two-dimensional materials, topological materials, analytical chemistry, chiral sensing, chiral optical force, and chiral light detection. Chiral SPs are a new type of optical phenomenon that have useful application potential in many fields and are worth exploring.

Optical Properties of Artemisinin and Its Derivatives.

Artemisinin and its derivatives are of great research value in biology. In this work, we study their chiral and optical properties. The multidimensional multifunction analysis method is used to analyze the linear and nonlinear optical processes (one-photon and two-photon absorption: OPA and TPA), electronic circular dichroism (ECD), and Raman optical activity (ROA) mechanisms under light excitation. Transition dipole moments (TDMs) and charge difference density (CDD) are used to describe the electromagnetic interaction between ECD and ROA when a substance is excited by light. The theoretical research results of the study show that the dioxygen atoms provide an intermediary for the transfer between charges and also enhance the role of the TDMs. This generalized chiral theory can not only explain the traditional sources of chirality but also distinguish whether the molecule has chirality when the chiral center is not obvious. By analyzing ROA and different vibration modes, we can clearly observe that each part of the molecule responds differently when excited.

Optical physics on chiral brominated azapirones: Bromophilone A and B.

In this work, we use the visualization method to study their intramolecular electric-magnetic interactions and reveal the physical mechanism of their electronic transition to explain the cause of the opposite ECD spectrum orientations. Azaphilone A and B are two chiral molecules, due to their differing chirality, the electronic circular dichroism (ECD) spectra of bromophilone A and B are very different at 431 nm. Based on the two-step transition process, the charge-transfer characteristics of the corresponding two-photon excited states of the two chiral molecules are analysed in detail by calculating the photoinduced charge transfer and electron-hole coherence in the two-photon absorption (TPA) process.

Photoinduced Charge Transfer in Push/Pull Systems of Two-Photon Absorption.

A series of stilbene derivatives have been constructed by modifying the stilbene systems with different H, CN, NH2, NMe2, and NO2 groups. In a vacuum, it was found that a redshift in the ultraviolet-visible spectrum occurred because of the enhancement of the donor/acceptor capabilities of this group, with the order of redshift being NO2 > NMe2 > CN > NH2 > H. For stilbene molecular systems, the peak of two-photon absorption (TPA) observed in the simulated spectra should be attributed to two transitions that are contributed by two excited states with similar energy. In the case of derivatives, such a transition is separated by energy, and two TPA peaks can be clearly observed (derivatives containing NO2 and NMe2 groups have two TPA peaks), where the magnitude of the separation is directly related to the intensity of the peripheral group. In addition, the S1 state is the intermediate state in the TPA transitions to both of the final excited states.