Electron Transfer Research Articles

Deciphering the Role of Inorganic Nanoparticles' Surface Functionalization on Biohybrid Microbial Photoelectrodes.

Shedding light on the interaction between inorganic nanoparticles (NPs) and living microorganisms is at the basis of the development of biohybrid technologies with improved performance. Au NPs have been shown to be able to improve the extracellular electron transfer (EET) in intact bacterial cells interfaced with an electrode; however, detailed information on the role of NP-surface properties in their interaction with bacterial membranes is still lacking. Herein, we unveil how the surface functionalization of Au NPs influences their interaction with photosynthetic bacteria, focusing on cell morphology, growth kinetics, NPs localization, and electrocatalytic performance. We show that functionalization of Au NPs with cysteine in the zwitterionic form results in a uniform NPs distribution in purple bacteria, specifically locating the NPs within the outer-membrane/periplasmic space of bacterial cells. These biohybrid cells, when coupled with an electrode, exhibit enhanced EET and increased (photo)current generation, paving the way for the future development of rationally designed biohybrid electrochemical systems.

Cyanide and chloroform detection through J-aggregates based aggregation induced emission probe with real sample applications

Isopthalamide based probe DPI has been synthesized by an easy two-step substitution reaction. Unique fluorescence properties of probe DPI were exploited for sensing of CNˉ and chloroform. Various spectroscopic techniques such as NMR, LC-MS, SEM, DLS, UV-Vis. and fluorescence spectroscopy in combination with DFT studies were used to confirm efficient detection of CN‾ through a non-covalent interaction of cyanide with probe. Furthermore, probe showed fluorescence emission at 360 nm which shifted significantly to 415 nm upon addition of water exhibiting unique AIE characteristics and formation of desired J-aggregates. Mechanistically, CN‾ and chloroform were selectively detected through fluorescence quenching with 9 nM and 0.2 % v/v limit of detection (LOD), respectively. Photoinduced electron transfer (PET) was proven to be involved as a sensing mechanism. Moreover, DPI exhibited interesting solvatochromism properties. DPI was proven to be a highly sensitive probe which showed solid-state and vapor phase on-field detection of CN‾. Similar sensing behavior of DPI probe towards CN‾ was seen in food and water samples.

Outstanding Activity and Durability of Supported NiCo2O4 Nanoparticles for Direct Ethanol Fuel Cells

ABSTRACTThe rational design of noble metal‐free electrocatalysts represents one of the basic stones for fuel cell development. With the exploration of eco‐friendly nanomaterials for the investigated alcohol oxidation process, nickel‐based electrodes have been recognized as the most auspicious anodes with promoted activity and stability. In this work, a series of NiCo2O4 nanoparticles were deposited onto graphite sheets (NiCo2O4/T) introducing varied proportions of cobalt oxide species. Co‐precipitation protocol of the respective metallic hydroxides onto the carbonaceous support was followed with consecutive annealing in an air atmosphere at 400°C. The fabricated mixed metallic oxide nanopowder was physically studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X‐ray analysis (EDX), X‐ray photoelectron spectroscopy (XPS), and selected area electron diffraction (SAED). Uniformly arranged nanoparticles were observed on graphite surface as evidenced by SEM and TEM. The cubic lattice structure of formed NiCo2O4 crystals was also confirmed by XRD through the defined peaks of binary metallic oxides clarifying their successful preparation scheme. The electrocatalytic properties of these NiCo2O4/T nanocatalysts were evaluated for oxidizing ethanol molecules in basic solution. Pronounced oxidation current densities were remarkably measured at NiCo2O4/T electrodes in relation to that at NiO/T. Differing the introduced cobalt oxide content into the synthesized nanocatalyst significantly controlled its catalytic performance. NiCo2O4/T‐20 exhibited the highest activity and stability among the prepared nanomaterials. Much decreased charge transfer resistances were also recorded at this electrode demonstrating its promoted electron transfer characteristics. This work could provide a reasonable route for the simple synthesis of comparable transition metallic oxides with promising attitudes for energy generation purposes.

Biomass Carbon Dots as Fluorescent Probes for Fast and Highly Selective Detection of Fe3 + in Water Media.

In this study, a novel fluorescent probe for the rapid and highly selective detection of Fe3 + based on biomass carbon dots (b-CDs) was developed. The b-CDs were obtained via one-step hydrothermal synthesis by utilizing laurel fallen leaves. And the as-synthesized b-CDs were applied for sensing Fe3+ based on fluorescence (FL) quenching effect both in water and phosphate buffer solution (PBS) with a wide linear range from 1 µM to 300 µM, the detection limits (LODs) respectively to be 0.34 µM in water and 0.48 µM in PBS solution. The FL intensity of b-CDs was quenched fleetly within 1min after adding Fe3+. The sensing mechanism of the b-CDs + Fe3+ system can be attributed to the internal filtration effect (IFE) mechanism and the electron transfer (ET) between b-CDs and Fe3+ in water, and only the IFE mechanism in PBS solution based on multiple experimental evidences. Moreover, the as-proposed probe was successfully adopted for monitoring Fe3+ in lake water and tap water samples. This research shows some merits of economic, simplicity, green, high selectivity, and quick response for Fe3+ determination, and provides an approach for the water quality monitoring of Fe3+ and the effective utilization of waste biological materials.

Linkage engineered poly(heptazine imide) optimizes charge transfer for efficient photocatalytic H2O2 production: Regulating oxygen reduction pathway

Photocatalytic H2O2 production via oxygen reduction reaction (ORR) is of great interest. However, the inferior charge transfer efficiency and the low 2e− ORR selectivity grossly constrain this process. Herein, we incorporated pyrimidine (PM) groups as linkers between heptazine units into the poly(heptazine imide) (PHI-PM). There was an augmented in-plane built-in electric field leading to elevated charge separation and transfer capabilities. Additionally, the incremental electron sink effect by PM groups prolonged the charge lifetime and fostered an efficient transfer of electrons from PM groups (electron trapping center) to −C≡N groups (oxygen adsorption center), significantly improving the activity and selectivity of 2e− ORR. Results indicated that the optimization of charge transfer greatly increased the proportion of two-step single-electron ORR, accelerating the reaction kinetics. Meanwhile, side-reaction 4e− ORR was inhibited attributed to the selective generation of •O2−. This work paved new avenues for regulating the pathway of photocatalytic ORR for H2O2 production.

Enhanced self-biased photocatalytic fuel cell performance by dual-photoelectrode with novel graphene-based substrate for tetracycline photodegradation and electricity production

In this study, a graphene-based dual-photoelectrode photocatalytic fuel cell (PFC) system, incorporating n-type ZnO photoanode and p-type Cu2O photocathode, has been meticulously designed and fabricated to achieve concurrent organic pollutant decomposition and electricity production. The rGO-ZnO｜rGO-Cu2O PFC system displayed superior photoelectrocatalytic performance, surpassing the comparative FTO-based PFC system. Notably, it achieved power density of 22.23 μW cm−2 maximumly, tetracycline hydrochloride (TCH) degradation efficiency of 74.0 % within 120 min, and exhibited long-term stability. This enhanced performance can give the credit to the larger active areas generated by the in-situ growth of photocatalytic materials in layered microstructure of graphene films, as well as the rapid electron transfer within graphene films. This study underscores the potential application of graphene films as electrode substrate materials, and introduces a strategy for achieving the diversification and optimization of electrode substrate material selection, ultimately facilitating the development of more efficient PFC systems.

Highly active Cu2O/CoCo-PBA S-scheme heterojunction for enhanced visible-light-driven hydrogen evolution

Prussian blue analogues is a unique class of organic-inorganic hybrid materials that have garnered significant attention in the field of photocatalysis due to their large specific surface area and abundant active sites. However, their potential is limited by the challenge of photogenerated charge carrier recombination. To address this issue, we successfully synthesized a tightly coupled Cu2O/CoCo-PBA S-scheme heterojunction catalyst using ultrasound-assisted and thermal treatment methods, aiming to reduce the recombination of photogenerated charge carriers. In this system, CoCo-PBA serves as the electron donor, while Cu2O acts as the electron acceptor. The closely coupled interface between these materials shortens the electron transfer distance. Under 10 W white light irradiation, the Cu2O/CoCo-PBA composite photocatalyst demonstrated remarkable hydrogen evolution activity, with a hydrogen production rate of 5.98 mmol⋅g⁻¹⋅h⁻¹, which is 6.4 times that of CoCo-PBA alone. This S-scheme heterojunction strategy lays the groundwork for the design and large-scale application of highly active visible-light-driven photocatalysts.

Developing oxygen vacancy-rich CuMn2O4/carbon dots dual-function nanozymes via Chan-Lam coupling reaction for the colorimetric/fluorescent determination of D-penicillamine

Defect engineering is a promising approach to construct high performance nanozymes due to its ability to regulate their physical and chemical properties. However, how to construct defects to improve the activity of nanozymes remains a challenge. Herein, for the first time, the Chan-Lam coupling reaction is used to construct the oxygen vacancy (OV)-rich CuMn2O4/carbon dots (CDs) (OV-CuMn2O4/CDs) dual-function nanozymes with fluorescent (FL) and oxidase-like properties, via regulating the low-valent metal ions (Cu+ and Mn2+) and Ov contents in the spinel CuMn2O4 and in-situ growth of β-cyclodextrin (β-CD)-derived CDs. Expectedly, relative to CuMn2O4, the OV-CuMn2O4/CDs exhibited 35.8%, 8.5%, and 14.6% rise in the contents of Cu+, Mn2+ and Ov, respectively. Abundant Ov provides more O2 adsorption/activation sites, and the charge transfer between Ov and metal atoms increases the charge density around metal atoms. This produces more low-valent metals (like Cu+ and Mn2+) to promote the electron transfer from metal to O atoms and O-O bond cleavage. Thus, the oxidase-like activity of OV-CuMn2O4/CDs is 4.1 times that of CuMn2O4. Also, the in-situ growth of β-CD-derived carbon dots on CuMn2O4 endows OV-CuMn2O4/CDs selective target recognition. Thus, a sensitive and selective colorimetric and fluorescence dual-mode method was established for determining D-penicillamine (D-PA), with the limit of detection of 0.25 and 0.048 μM, respectively. The method was applied to D-PA determination in real samples. This work demonstrates the Chan-Lam coupling reaction can be used to construct high performance nanozymes for developing dual-mode sensor for the detection of targets.

An Electron Bridge of Shared Atoms Mediated Cs3Bi2Br9/Bi2WO6 Z‐Scheme Heterojunction for Photocatalytic CO2 Reduction

AbstractConverting clean solar energy into chemical energy through artificial photosynthesis is an effective solution to solve the energy and environmental issues. Here, we report a Cs3Bi2Br9/Bi2WO6 (CBB/BWO) Z‐scheme heterojunction constructed via electrostatic self‐assembly, which facilitates efficient separation of photogenerated carriers and ensures the corresponding redox capacity of both components. By sharing Bi atoms, a Br−Bi−O bond is established between CBB and BWO, serving as an “electron bridge”. The electrons generated by BWO are efficiently channeled to CBB through the heterojunction‐formed “electron bridge”, thereby achieving effective photocatalytic CO2 reduction. Under simulated sunlight conditions, it exhibits the highest CO yield of 72.52 μmol g−1 (without the addition of any precious metal, photosensitizers or sacrifices), which is approximately 7‐fold and 18‐fold greater than that of pure CBB and BWO, respectively. This work provides a more profound comprehension of the regulation of electron transfer through interfacial chemical bonds, thereby proposing a promising strategy for the development of efficient heterojunction photocatalysts for CO2 photoreduction.

Interfacial Conductor-Modulated Low-Triggered Potential Electrochemiluminescence from Conjugated Polymers for Bioanalysis.

Polyfluorene and its derivatives (PFs) are extremely appealing electrochemiluminescence (ECL) illuminants thanks to their easy modification, high quantum yield, excellent photostability, and nontoxicity, exhibiting great application potential in ECL sensing and imaging. Unfortunately, most reported PFs-based ECL bioanalysis generally exhibited high triggering potential (>1.0 V vs Ag/AgCl), which introduced undesirable electrochemical interference to adversely affect the sensitivity and accuracy of biological analysis. This work innovatively exploited poly(3,4-ethylenedioxythiophene) (PEDOT) as an interfacial conductor to modulate the low ECL triggering potential of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadazole)] (PFBT) nanoparticles (NPs). The unique conductivity of in situ electrodeposited PEDOT promoted electron transfer between PFBT NPs and coreactant tripropylamine (TPrA), negatively shifting the ECL triggering potential of PFBT NPs from +1.22 to +0.78 V. The PFBT NPs/PEDOT coupled the localized hybridization chain reaction (LHCR) circuits to achieve a specific and sensitive ECL detection of malathion (MAL), and a low limit of detection (LOD) of 22 fg/mL was obtained. The interfacial conductor provides inspiration for creating the low ECL triggering potential. PFBT NPs-coupled PEDOT builds a low ECL triggering potential of the PFs-based platform for pesticide residue analysis with low interference and high sensitivity.

Electron transfer in biological systems.

Examples of how metalloproteins feature in electron transfer processes in biological systems are reviewed. Attention is focused on the electron transport chains of cellular respiration and photosynthesis, and on metalloproteins that directly couple electron transfer to a chemical reaction. Brief mention is also made of extracellular electron transport. While covering highlights of the recent and the current literature, this review is aimed primarily at introducing the senior undergraduate and the novice postgraduate student to this important aspect of bioinorganic chemistry.

Electron Transfer Capability in Atomic Hydrogen Reactions for Imidazole Groups Bound to the Insulating Alkanethiolate Layer on Au(111).

The charge transfer capability associated with chemical reactions at metal-organic interfaces was studied via the atomic H addition reaction for an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) film on Au(111) at room temperature, using near-edge X-ray absorption fine structure spectroscopy, infrared reflection absorption spectroscopy, work function measurements, and density functional theory calculations. The imidazolium cation is a stable species in liquids; therefore, it is pertinent to determine whether the hydrogenation reactions of the imidazole groups produce imidazolium cations accompanied by electron transfer to the Au substrate, even in the absence of solvate and/or counterions on the insulating alkanethiolate layer. The experiments made it clear that the imidazolium moieties were formed during the irradiation of Im-SAM with atomic H. Theoretical model calculations also revealed that the total energies and molecular orbital levels satisfied the imidazolium cation formation associated with electron transfer. In a detailed analysis of the work function change depending on H irradiation, we confirmed that some of the imidazolium radicals became cations in Im-SAM.

Proton Ionic Liquid Modulates Hydrogen Coverage and Subsurface Absorbed Hydrogen to Enhance Pd Metallene Electrocatalytic Semi-hydrogenation of Alkynols.

Electrochemical semi-hydrogenation of alkynols to produce high-value alkenols is a green and sustainable approach. Although Pd can exhibit excellent semi-hydrogenation properties, its intrinsic mechanism still lacks in-depth study. Herein, a proton ionic liquid (PIL)-modified Pd metallene (Pdene@PIL) is synthesized for the electrocatalytic semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE). The PIL modification of Pdene@PIL resulted in an MBY conversion of 96.1% and MBE selectivity of 97.2%, respectively. Theoretical calculations indicate the electron transfer between Pdene and PIL, leading to easier adsorption of MBY on the Pd surface. The d-band center of Pdene@PIL shifts away from the Fermi level, which weakens the adsorption of over-hydrogenated intermediates. At the same time, the PIL modification facilitates the adsorption of surface-adsorbed hydrogen (H*ads) and inhibits the formation of subsurface-absorbed hydrogen (H*abs). In particular, the PIL modification optimizes Hads* coverage, reduces the reaction energy of the rate-determining step (C5H8O*-C5H9O*), and inhibits HER. The reduction of H*abs formation inhibits the transfer of Pd to PdHx and suppresses the over-hydrogenation. This work provides new insights into the modulation of H* to enhance the alkynol electrocatalytic semi-hydrogenation reaction (ESHR) process from the perspective of surface modification.

Supraparticles from Cubic Iron Oxide Nanoparticles: Synthesis, Polymer Encapsulation, Functionalization, and Magnetic Properties.

Supraparticles (SPs) consisting of superparamagnetic iron oxide nanoparticles (SPIONs) are of great interest for biomedical applications and magnetic separation. To enable their functionalization with biomolecules and to improve their stability in aqueous dispersion, polymer shells are grown on the SPs' surface. Robust polymer encapsulation and functionalization is achieved via atom transfer radical polymerization (ATRP), improving the reaction control compared to free radical polymerizations. This study presents the emulsion-based assembly of differently sized cubic SPIONs (12-30 nm) into SPs with diameters ranging from ∼200 to ∼400 nm using dodecyltrimethylammonium bromide (DTAB) as the surfactant. The successful formation of well-defined spherical SPs depends upon the method used for mixing the SPION dispersion with the surfactant solution and requires the precise adjustment of the surfactant concentration. After purification, the SPs are encapsulated by growing surface-grafted polystyrene shells via activators generated by electron transfer (AGET) ATRP. The polymer shell can be decorated with functional groups (azide and carboxylate) using monomer blends for the polymerization reaction. When the amount of the monomer is varied, the shell thickness as well as the interparticle distances between the encapsulated SPIONs can be tuned with nanometer-scale precision. Small-angle X-ray scattering (SAXS) reveals that cubic SPIONs form less ordered assemblies within the SPs than spherical SPIONs. As shown by vibrating sample magnetometer measurements, the encapsulated SPs feature the same superparamagnetic behavior as their SPION building blocks. The saturation magnetization ranges between 10 and 30 emu/g and depends upon the nanocubes' size and phase composition.

Immobilization of Membrane-Associated Protein Complexes on SERS-Active Nanomaterials for Structural and Dynamic Characterization.

Exploring the structural basis of membrane proteins is significant for a deeper understanding of protein functions. In situ analysis of membrane proteins and their dynamics, however, still challenges conventional techniques. Here we report the first attempt to immobilize membrane protein complexes on surface-enhanced Raman scattering (SERS)-active supports, titanium dioxide-coated silver (Ag@TiO2) nanoparticles. Biocompatible immobilization of microsomal monooxygenase complexes is achieved through lipid fission and fusion. SERS activity of the Ag@TiO2 nanoparticles enables in situ monitoring of protein-protein electron transfer and enzyme catalysis in real time. Through SERS fingerprints of the monooxygenase redox centers, the correlations between these protein-ligand interactions and reactive oxygen species generation are revealed, providing novel insights into the molecular mechanisms underlying monooxygenase-mediated apoptotic regulation. This study offers a novel strategy to explore structure-function relationships of membrane protein complexes and has the potential to advance the development of novel reactive oxygen species-inducing drugs for cancer therapy.

Facile modification of TiO2 as S-Scheme multifunctional materials for environmental protection and energy-storage applications

This paper reports a simple one-step modification of commercial TiO2 with a conducting polytrimethoxyslilypropyl aniline (PTMSPA, a polyaniline derivative having silyl networks) to have multi-functional (photocatalytic, optical, pseudocapacitive, hydrophobic, porous, antibacterial, and electromagnetic interference shielding (EMI)) properties and demonstrates associated applications. We present the S-Scheme heterojunction (SHJ) formation between TiO2 and PTMSPA through band position alignments and designate the resultant TiO2 - TiO2- based SHJ multifunctional materials as MF-TSSM. The internal electric field that is generated at the interface facilitates the transportation of the photogenerated electron transfer . The XRD pattern of MF-TSSM exhibits mainly the peaks of anatase TiO2. The TEM image of MF-TSSM indicates that the TiO2 particles are spherical in shape with sizes showing variations in diameters ranging from 60 nm to 250 nm depending on the experimental conditions of preparation and TiO2 particles are homogeneously distributed within the PTMSPA matrix. The optical energy band gap of MF-TSSM is 1.60 eV, a much lower value than PTMSPA (3.02 eV), suggesting that the composite formation between TiO2 and PTMSPA. The contact angle of MF-TSSM is significantly increased to 47.1 ° from 8.0 of TiO2, informing the increase of hydrophobic characteristics. The rate constant (k) for methylene blue photodegradation was 0.030 min-1, and 0.010 min-1 for MF-TSSM and pristine TiO2, respectively, The MF-TSSM composite exhibits a higher specific capacitance value (28.7 F/g) than TMSPA (21.1 F/g). At a frequency of 0.42 THz, MF-TSSM and PTMSPA exhibit return loss features indicating good EMI shielding performance. The MF-TSSM has been tested against two different Gram-positive and Gram-negative bacterial strains. The nanoparticles were evaluated at doses of 10, 20, 40, and 80 µg/ml. The results indicated that Klebsiella pneumoniae demonstrated a greater zone of inhibition, ranging from 9 mm at 10 µg/ml to 23 mm at 80 µg/ml, indicating increased susceptibility. Pseudomonas aeruginosa exhibited reduced inhibition zones, ranging from 10 mm at 10 µg/ml to 14 mm at 80 µg/ml, indicating increased resistance. The excellent effectiveness of MF-TSSM against various Gram-positive and Gram-negative pathogenic bacteria is explained by the interaction between reactive oxygen species and the cellular components of the bacteria as well the electrostatic interaction arising between positive charges in TMSPA and negative charges in the cell components, resulting in notable cytotoxicity and damage to the bacterial cells. The research underscores the capability of these modified TiO₂ nanoparticles in addressing bacterial infections, with efficiency differing by bacterial strain.

A Family of Twisted Chiral Engineered Inorganic Nanoarchitectures.

Chiral inorganic materials possess unique asymmetric properties that could significantly impact various fields. However, their practical application has been hindered by challenges in creating structurally robust chiral materials. We report the synthesis of well-defined chiral-shaped hollow cobalt oxide nanostructures, extendable to a family of chalcogenides including sulfide, selenide, and telluride through topological transformations. Taking chiral cobalt oxide nanostructures as a representative material, we demonstrate precise control over their chiral architectures, enabling fine-tuning of parameters, such as twist degrees, handedness, and compositions. These chiral nanostructures exhibit high spin selectivity effects that influence the electron transfer processes in catalytic reactions. Leveraging this spin-selective behavior, the chiral cobalt oxide nanoarchitectures demonstrate enhanced electrocatalytic performance in the oxygen evolution reaction compared to their achiral counterparts. Our findings not only expand the library of chiral inorganic materials but also advance the application of chiral effects in fields such as catalysis, spintronics, and beyond.

Fabrication of pyridine incorporated and O-doped g-C3N4/COF: A type-II heterojunction for enhanced hydrogen production under visible light irradiation

The fabrication of heterojunction photocatalysts is important for achieving highly efficient electron transfer, charge separation, and catalytic activity. In this study, we report the successful creation of a type II heterojunction between pyridine incorporated and O-doped g-C3N4 (POCN) and a covalent organic framework (COF). The heterojunction formation significantly reduced the fluorescence intensity of the POCN/COF, indicating effective separation of electron-hole pairs. Additionally, POCN/COF demonstrated excellent interface charge transfer resistance and photocurrent response. Its hydrogen production rate was remarkably high at 3500 μmol g⁻1 h⁻1, about 1.6 times that of pure COF (2200 μmol g⁻1 h⁻1) and 3.5 times that of the physical mixture (1000 μmol g⁻1 h⁻1), and it also exhibited enhanced stability. This indicates that it can be effectively fabricated into a heterojunction of POCN and COF. The optimal value for adding POCN was approximately 5 wt% of COF. This demonstrates greater activity compared to other composite catalysts made from graphitic carbon nitride and COF. This study presents a valuable approach for fabricating reusable heterojunction photocatalytic systems and efficiently generating hydrogen from natural energy sources.

One‐Stone‐For‐Three‐Birds Strategy Using a Fullerene Modifier for Efficient and Stable Inverted Perovskite Solar Cells

AbstractThe electron extraction from perovskite/C60 interface plays a crucial role in influencing the photovoltaic performance of inverted perovskite solar cells (PSCs). Here, we develop a one‐stone‐for‐three‐birds strategy via employing a novel fullerene derivative bearing triple methyl acrylate groups (denoted as C60‐TMA) as a multifunctional interfacial layer to optimize electron extraction at the perovskite/C60 interface. It is found that the C60‐TMA not only passivates surface defects of perovskite via coordination interactions between C=O groups and Pb2+ cations but also bridge electron transfer between perovskite and C60. Moreover, it effectively induces the secondary grain growth of the perovskite film through strong bonding effect, and this phenomenon has never been observed in prior art reports on fullerene related studies. The combination of the above three upgrades enables improved perovskite film quality with increased grain size and enhanced crystallinity. With these advantages, C60‐TMA treated PSC devices exhibit a much higher power conversion efficiency (PCE) of 24.89 % than the control devices (23.66 %). Besides, C60‐TMA benefits improved thermal stability of PSC devices, retaining over 90 % of its initial efficiency after aging at 85 °C for 1200 h, primarily due to the reinforced interfacial interactions and improved perovskite film quality.

Targeted Modulation of Photocatalytic Hydrogen Evolution Activity by Nickel-Substituted Rubredoxin through Functionalized Ruthenium Phototriggers.

Light-driven hydrogen evolution is a promising means of sustainable energy production to meet global energy demand. This study investigates the photocatalytic hydrogen evolution activity of nickel-substituted rubredoxin (NiRd), an artificial hydrogenase mimic, covalently attached to a ruthenium phototrigger (RuNiRd). By systematically modifying the para-substituents on Ru(II) polypyridyl complexes, we sought to optimize the intramolecular electron transfer processes within the RuNiRd system. A series of electron-donating and electron-withdrawing groups were introduced to tune the photophysical, photochemical, and electrochemical properties of the ruthenium complexes. Our findings reveal that electron-donating substituents can increase the hydrogen evolution capabilities of the artificial enzyme to a point; however, the complexes with the most electron-donating substituents suffer from short lifetimes and inefficient reductive quenching, rendering them inactive. The present work highlights the intricate balance required between driving force, lifetime, and quenching efficiency for effective light-driven catalysis, providing valuable insights into the design of artificial enzyme-photosensitizer constructs.