Harvesting electrons and holes from photodriven symmetry-breaking charge separation within a perylenediimide photosynthetic model dimer.

Understanding how to utilize symmetry-breaking charge separation (SB-CS) offers a path toward increasingly efficient light-harvesting technologies. This process plays a central role in the first step of photosynthesis, in which the dimeric "special pair" of the photosynthetic reaction center enters a coherent SB-CS state after photoexcitation. Previous research on SB-CS in both biological and synthetic chromophore dimers has focused on increasing the efficiency of light-driven processes. In a chromophore dimer undergoing SB-CS, the energy of the radical ion pair product is nearly isoenergetic with that of the lowest excited singlet (S1) state of the dimer. This means that very little energy is lost from the absorbed photon. In principle, the relatively high energy electron and hole generated by SB-CS within the chromophore dimer can each be transferred to adjacent charge acceptors to extend the lifetime of the electron-hole pair, which can increase the efficiency of solar energy conversion. To investigate this possibility, we have designed a bis-perylenediimide cyclophane (mPDI2) covalently linked to a secondary electron donor, peri-xanthenoxanthene (PXX) and a secondary electron acceptor, partially fluorinated naphthalenediimide (FNDI). Upon selective photoexcitation of mPDI2, transient absorption spectroscopy shows that mPDI2 undergoes SB-CS, followed by two secondary charge transfer reactions to generate a PXX•+-mPDI2-FNDI•- radical ion pair having a nearly 3 µs lifetime. This strategy has the potential to increase the efficiency of molecular systems for artificial photosynthesis and photovoltaics.

Molecular oxidation-reduction junctions for artificial photosynthetic overall reaction.

Constructing redox semiconductor heterojunction photocatalysts is the most effective and important means to complete the artificial photosynthetic overall reaction (i.e., coupling CO2 photoreduction and water photo-oxidation reactions). However, multiphase hybridization essence and inhomogeneous junction distribution in these catalysts extremely limit the diverse design and regulation of the modes of photogenerated charge separation and transfer pathways, which are crucial factors to improve photocatalytic performance. Here, we develop molecular oxidation-reduction (OR) junctions assembled with oxidative cluster (PMo12, for water oxidation) and reductive cluster (Ni5, for CO2 reduction) in a direct (d-OR), alternant (a-OR), or symmetric (s-OR) manner, respectively, for artificial photosynthesis. Significantly, the transfer direction and path of photogenerated charges between traditional junctions are obviously reformed and enriched in these well-defined crystalline catalysts with monophase periodic distribution and thus improve the separation efficiency of the electrons and holes. In particular, the charge migration in s-OR shows a periodically and continuously opposite mode. It can inhibit the photogenerated charge recombination more effectively and enhance the photocatalytic performance largely when compared with the traditional heterojunction models. Structural analysis and density functional theory calculations disclose that, through adjusting the spatial arrangement of oxidation and reduction clusters, the energy level and population of the orbitals of these OR junctions can be regulated synchronously to further optimize photocatalytic performance. The establishment of molecular OR junctions is a pioneering important discovery for extremely improving the utilization efficiency of photogenerated charges in the artificial photosynthesis overall reaction.

Toward Photosynthetic Mammalian Cells through Artificial Endosymbiosis.

Photosynthesis in plants occurs within specialized organelles known as chloroplasts, which are postulated to have originated through endosymbiosis with cyanobacteria. In nature, instances are also observed wherein specific invertebrates engage in symbiotic relationships with photosynthetic bacteria, allowing them to subsist as photoautotrophic organisms over extended durations. Consequently, the concept of engineering artificial endosymbiosis between mammalian cells and cyanobacteria represents a promising avenue for enabling photosynthesis in mammals. The study embarked with the identification of Synechocystis PCC 6803 as a suitable candidate for establishing a long-term endosymbiotic relationship with macrophages. The cyanobacteria internalized by macrophages exhibited the capacity to rescue ATP deficiencies within their host cells under conditions of illumination. Following this discovery, a membrane-coating strategy is developed for the intracellular delivery of cyanobacteria into non-macrophage mammalian cells. This pioneering technique led to the identification of human embryonic kidney cells HEK293 as optimal hosts for achieving sustained endosymbiosis with Synechocystis PCC 6803. The study offers valuable insights that may serve as a reference for the eventual achievement of artificial photosynthesis in mammals.

Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations.

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH2-MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonance spectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min-1. Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to the metal-organic framework surface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. The constructed photo-enzyme coupled system successfully combines enzyme catalysis' selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

Hollow Plasmonic P-Metal-N S-Scheme Heterojunction Photoreactor with Spatially Separated Dual Cocatalysts toward Artificial Photosynthesis.

Semiconductor-based step-scheme (S-scheme) heterojunctions possess many merits toward mimicking natural photosynthesis. However, their applications for solar-to-chemical energy conversion are hindered by inefficient charge utilization and unsatisfactory surface reactivity. Herein, two synergistic protocols are demonstrated to overcome these limitations based on the construction of a hollow plasmonic p-metal-n S-scheme heterojunction photoreactor with spatially separated dual noble-metal-free cocatalysts. On one side, plasmonic Au, inserted into the heterointerfaces of CuS@ZnIn2 S4 core-shell nanoboxes, not only accelerates the transfer and recombination of useless charges, enabling a more thorough separation of useful ones for CO2 reduction and H2 O oxidation but also generates hot electrons and holes, respectively injects them into ZnIn2 S4 and CuS, further increasing the number of active carriers participating in redox reactions. On the other side, Fe(OH)x and Ti3 C2 cocatalysts, separately located on the CuS and ZnIn2 S4 surface, enrich the redox sites, adjust the reduction potential and pathway for selective CO2 -to-CH4 transformation, and balance the transfer and consumption of photocarriers. As expected, significantly enhanced activity and selectivity in CH4 production are achieved by the smart design along with nearly stoichiometric ratios of reduction and oxidation products. This study paves the way for optimizing artificial photosynthetic systems via rational interfacial channel introduction and surface cocatalyst modification.

Optimizing Photocatalytic H2 Production by Introduction of Pyrazinyls to WRCs and a New tris-Rhenium Photosensitizer.

The replacement of pyridyl by pyrazinyl in ligands of polypyridyl-based cobalt water reducing catalysts (WRC) shifts reduction potentials anodically. Together with a new, trinuclear ReI photosensitizer, these WRCs show strongly improved photocatalytic performances in turnover numbers (TONs) and maximal H2 evolution rate. Depending on the catalyst structure, up to 65 kTONs at 1 µM WRC concentration were reached. Under electrocatalytic conditions in both DMF and H2O, one of the reported WRCs displays remarkable stability, producing H2 steadily over 21 and 14 d, respectively.

Influence of Donor-Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores.

In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2'-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.

Poly(dehydroalanine)-Based Hydrogels as Efficient Soft Matter Matrices for Light-Driven Catalysis.

Soft matter integration of photosensitizers and catalysts provides promising solutions to developing sustainable materials for energy conversion. Particularly, hydrogels bring unique benefits, such as spatial control and 3D-accessibility of molecular units, as well as recyclability. Herein, the preparation of polyampholyte hydrogels based on poly(dehydroalanine) (PDha) is reported. Chemically crosslinked PDha with bis-epoxy poly(ethylene glycol) leads to a transparent, self-supporting hydrogel. Due to the ionizable groups on PDha, this 3D polymeric matrix can be anionic, cationic, or zwitterionic depending on the pH value, and its high density of dynamic charges has a potential for electrostatic attachment of charged molecules. The integration of the cationic molecular photosensitizer [Ru(bpy)3 ]2+ (bpy = 2,2'-bipyridine) is realized, which is a reversible process controlled by pH, leading to light harvesting hydrogels. They are further combined with either a thiomolybdate catalyst ([Mo3 S13 ]2- ) for hydrogen evolution reaction (HER) or a cobalt polyoxometalate catalyst (Co4 POM = [Co4 (H2 O)2 (PW9 O34 )2 ]10- ) for oxygen evolution reaction (OER). Under the optimized condition, the resulting hydrogels show catalytic activity in both cases upon visible light irradiation. In the case of OER, higher photosensitizer stability is observed compared to homogeneous systems, as the polymer environment seems to influence decomposition pathways.

Acetogenic bacteria utilize light-driven electrons as an energy source for autotrophic growth.

Acetogenic bacteria use cellular redox energy to convert CO2 to acetate using the Wood-Ljungdahl (WL) pathway. Such redox energy can be derived from electrons generated from H2 as well as from inorganic materials, such as photoresponsive semiconductors. We have developed a nanoparticle-microbe hybrid system in which chemically synthesized cadmium sulfide nanoparticles (CdS-NPs) are displayed on the cell surface of the industrial acetogen Clostridium autoethanogenum The hybrid system converts CO2 into acetate without the need for additional energy sources, such as H2, and uses only light-induced electrons from CdS-NPs. To elucidate the underlying mechanism by which C. autoethanogenum uses electrons generated from external energy sources to reduce CO2, we performed transcriptional analysis. Our results indicate that genes encoding the metal ion or flavin-binding proteins were highly up-regulated under CdS-driven autotrophic conditions along with the activation of genes associated with the WL pathway and energy conservation system. Furthermore, the addition of these cofactors increased the CO2 fixation rate under light-exposure conditions. Our results demonstrate the potential to improve the efficiency of artificial photosynthesis systems based on acetogenic bacteria integrated with photoresponsive nanoparticles.

Mechanism of the formation of proton transfer pathways in photosynthetic reaction centers.

In photosynthetic reaction centers from purple bacteria (PbRCs) from Rhodobacter sphaeroides, the secondary quinone QB accepts two electrons and two protons via electron-coupled proton transfer (PT). Here, we identify PT pathways that proceed toward the QB binding site, using a quantum mechanical/molecular mechanical approach. As the first electron is transferred to QB, the formation of the Grotthuss-like pre-PT H-bond network is observed along Asp-L213, Ser-L223, and the distal QB carbonyl O site. As the second electron is transferred, the formation of a low-barrier H-bond is observed between His-L190 at Fe and the proximal QB carbonyl O site, which facilitates the second PT. As QBH2 leaves PbRC, a chain of water molecules connects protonated Glu-L212 and deprotonated His-L190 forms, which serves as a pathway for the His-L190 reprotonation. The findings of the second pathway, which does not involve Glu-L212, and the third pathway, which proceeds from Glu-L212 to His-L190, provide a mechanism for PT commonly used among PbRCs.

Chromatophores efficiently promote light-driven ATP synthesis and DNA transcription inside hybrid multicompartment artificial cells.

The construction of energetically autonomous artificial protocells is one of the most ambitious goals in bottom-up synthetic biology. Here, we show an efficient manner to build adenosine 5'-triphosphate (ATP) synthesizing hybrid multicompartment protocells. Bacterial chromatophores from Rhodobacter sphaeroides accomplish the photophosphorylation of adenosine 5'-diphosphate (ADP) to ATP, functioning as nanosized photosynthetic organellae when encapsulated inside artificial giant phospholipid vesicles (ATP production rate up to ∼100 ATP∙s-1 per ATP synthase). The chromatophore morphology and the orientation of the photophosphorylation proteins were characterized by cryo-electron microscopy (cryo-EM) and time-resolved spectroscopy. The freshly synthesized ATP has been employed for sustaining the transcription of a DNA gene, following the RNA biosynthesis inside individual vesicles by confocal microscopy. The hybrid multicompartment approach here proposed is very promising for the construction of full-fledged artificial protocells because it relies on easy-to-obtain and ready-to-use chromatophores, paving the way for artificial simplified-autotroph protocells (ASAPs).

In-Cell Engineering of Protein Crystals into Hybrid Solid Catalysts for Artificial Photosynthesis.

The emergence of protein-based crystalline materials offers promising opportunities in enzyme immobilization. However, the current systems used for encapsulation of protein crystals are limited to either exogenous small molecules or monomeric proteins. In this work, polyhedra crystals were used to simultaneously encapsulate the foreign enzymes FDH and the organic photocatalyst eosin Y. These hybrid protein crystals are prepared easily by cocrystallization within a cell without a requirement for complex purification processes because they spontaneously form 1 µm scale solid particles. After immobilization within protein crystals, the recombinant FDH is recyclable and thermally stable and maintains 94.4% activity compared to the free enzyme. In addition, the incorporation of eosin Y endows the solid catalyst with CO2-formate conversion activity based on a cascade reaction. This work indicates that engineering protein crystals by both in vivo and in vitro strategies will provide robust and environmentally friendly solid catalysts for artificial photosynthesis.

Time-Resolved Mechanistic Depiction of Photoinduced CO2 Reduction Catalysis on a Urea-Modified Iron Porphyrin.

The development of functional artificial photosynthetic devices relies on the understanding of mechanistic aspects involved in specialized photocatalysts. Modified iron porphyrins have long been explored as efficient catalysts for the light-induced reduction of carbon dioxide (CO2) towards solar fuels. In spite of the advancements in homogeneous catalysis, the development of the next generation of catalysts requires a complete understanding of the fundamental photoinduced processes taking place prior to and after activation of the substrate by the catalyst. In this work, we employ a state-of-the-art nanosecond optical transient absorption spectroscopic setup with a double excitation capability to induce charge accumulation and trigger the reduction of CO2 to carbon monoxide (CO). Our biomimetic system is composed of a urea-modified iron(III) tetraphenylporphyrin (UrFeIII) catalyst, the prototypical [Ru(bpy)3]2+ (bpy=2,2'-bipyridine) used as a photosensitizer, and sodium ascorbate as an electron donor. Under inert atmosphere, we show that two electrons can be successively accumulated on the catalyst as the fates of the photogenerated UrFeII and UrFeI reduced species are tracked. In the presence of CO2, the catalytic cycle is kick-started providing further evidence on CO2 activation by the UrFe catalyst in its formal FeI oxidation state.

Ordering Bimetallic Cu-Pd Catalysts onto Orderly Mesoporous SrTiO3-Crystal Nanotubular Networks for Efficient Carbon Dioxide Photoreduction.

Artificial photosynthesis of fuels has garnered significant attention, with SrTiO3 emerging as a potential candidate for photocatalysis due to its exceptional physicochemical properties. However, selectively converting CO2 into fuels with desired reaction products remains a grand challenge. Herein, we design an updated method via an aging strategy based on the electrospinning technique to synthesize a single-crystalline Al-doped SrTiO3 nanotubular networks with self-assembled orderly mesopores, further modified by Cu-Pd alloy. It exhibits both high crystallinity and superior cross-linked mesoporous structures, effectively facilitating charge carrier transfer, photon utilization, and mass transfer, with a remarkable enhancement from 0.025 mmol h-1 m-2 to 1.090 mmol h-1 m-2 in the CO production rate. Meanwhile, the ordered arrangement of Cu and Pd atoms on the (111) surface can promote the rate-determining step (*CO2 to *COOH), which is also responsible for its good activity. The presence of CuO in the reaction confers a significant advantage for CO desorption, leading to a remarkable CO selectivity of 95.54 %. This work highlights new insights into developing advanced heterogeneous photocatalysts.

Pivotal Role of Geometry Regulation on O-O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts.

In this study, we highlight the impact of catalyst geometry on the formation of O-O bonds in Cu2 and Fe2 catalysts. A series of Cu2 complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, the catalytic performance of these Cu2 complexes is enhanced as their molecular skeletons become more rigid, which contrasts with the behavior observed in our previous investigation with Fe2 analogs. Moreover, mechanistic studies reveal that the reactivity of the bridging O atom results in distinct pathways for O-O bond formation in Cu2 and Fe2 catalysts. In Cu2 systems, the coupling takes place between a terminal CuIII -OH and a bridging µ-O⋅ radical. Whereas in Fe2 systems, it involves the coupling of two terminal Fe-oxo entities. Furthermore, an in-depth structure-activity analysis uncovers the spatial geometric prerequisites for the coupling of the terminal OH with the bridging µ-O⋅ radical, ultimately leading to the O-O bond formation. Overall, this study emphasizes the critical role of precisely adjusting the spatial geometry of catalysts to align with the O-O bonding pathway.

Toward a Comprehensive Understanding of Amorphous Photocatalysts: Fundamental Hypotheses and Applications in CO2 Photoreduction.

In principle, photocatalytic activity can be precisely controlled with crystalline catalysts. However, an amorphous photocatalyst could be a viable candidate for CO2 photoreduction to form value-added products. The amorphous phase is currently part of the crystalline material in several ongoing CO2 photoreduction studies. Additionally, no study indicates the amorphous material required for overall CO2 photoreduction. This perspective review article highlights fundamental assumptions that are necessary to gain insights and understand the effectiveness of amorphous photocatalysts for CO2 photoreduction. We start with basic ideas and theories about these materials, including light harvesting, variable coordination number, and the interaction of CO2 molecules with the amorphous catalytic surface. To understand the prospects of the amorphous photocatalyst, we explore machine learning with EXAFS. Furthermore, we discuss product selectivity and regeneration of photocatalysts in detail. Finally, we briefly review the work in progress on amorphous materials and compare it to that on crystalline ones.

A stable dye-sensitized photoelectrosynthesis cell mediated by a NiO overlayer for water oxidation.

In the development of photoelectrochemical cells for water splitting or CO2 reduction, a major challenge is O2 evolution at photoelectrodes that, in behavior, mimic photosystem II. At an appropriate semiconductor electrode, a water oxidation catalyst must be integrated with a visible light absorber in a stable half-cell configuration. Here, we describe an electrode consisting of a light absorber, an intermediate electron donor layer, and a water oxidation catalyst for sustained light driven water oxidation catalysis. In assembling the electrode on nanoparticle SnO2/TiO2 electrodes, a Ru(II) polypyridyl complex was used as the light absorber, NiO was deposited as an overlayer, and a Ru(II) 2,2'-bipyridine-6,6'-dicarboxylate complex as the water oxidation catalyst. In the final electrode, addition of the NiO overlayer enhanced performance toward water oxidation with the final electrode operating with a 1.1 mA/cm2 photocurrent density for 2 h without decomposition under one sun illumination in a pH 4.65 solution. We attribute the enhanced performance to the role of NiO as an electron transfer mediator between the light absorber and the catalyst.

Acquirement of water-splitting ability and alteration of the charge-separation mechanism in photosynthetic reaction centers.

In photosynthetic reaction centers from purple bacteria (PbRC) and the water-oxidizing enzyme, photosystem II (PSII), charge separation occurs along one of the two symmetrical electron-transfer branches. Here we report the microscopic origin of the unidirectional charge separation, fully considering electron-hole interaction, electronic coupling of the pigments, and electrostatic interaction with the polarizable entire protein environments. The electronic coupling between the pair of bacteriochlorophylls is large in PbRC, forming a delocalized excited state with the lowest excitation energy (i.e., the special pair). The charge-separated state in the active branch is stabilized by uncharged polar residues in the transmembrane region and charged residues on the cytochrome c2 binding surface. In contrast, the accessory chlorophyll in the D1 protein (ChlD1) has the lowest excitation energy in PSII. The charge-separated state involves ChlD1•+ and is stabilized predominantly by charged residues near the Mn4CaO5 cluster and the proceeding proton-transfer pathway. It seems likely that the acquirement of water-splitting ability makes ChlD1 the initial electron donor in PSII.

Crystallographic Effects of GaN Nanostructures in Photoelectrochemical Reaction.

Tuning the surface structure of the photoelectrode provides one of the most effective ways to address the critical challenges in artificial photosynthesis, such as efficiency, stability, and product selectivity, for which gallium nitride (GaN) nanowires have shown great promise. In the GaN wurtzite crystal structure, polar, semipolar, and nonpolar planes coexist and exhibit very different structural, electronic, and chemical properties. Here, through a comprehensive study of the photoelectrochemical performance of GaN photocathodes in the form of films and nanowires with controlled surface polarities we show that significant photoelectrochemical activity can be observed when the nonpolar surfaces are exposed in the electrolyte, whereas little or no activity is measured from the GaN polar c-plane surfaces. The atomic origin of this fundamental difference is further revealed through density functional theory calculations. This study provides guideline on crystal facet engineering of metal-nitride photo(electro)catalysts for a broad range of artificial photosynthesis chemical reactions.

Molecular Characteristics of Water-Insoluble Tin-Porphyrins for Designing the One-Photon-Induced Two-Electron Oxidation of Water in Artificial Photosynthesis.

Faced with the new stage of water oxidation by molecular catalysts (MCs) in artificial photosynthesis to overcome the bottle neck issue, the "Photon-flux density problem of sunlight," a two-electron oxidation process forming H2O2 in place of the conventional four-electron oxidation evolving O2 has attracted much attention. The molecular characteristics of tin(IV)-tetrapyridylporphyrin (SnTPyP), as one of the most promising MCs for the two-electron water oxidation, has been studied in detail. The protolytic equilibria among nine species of SnTPyP, with eight pKa values on the axial ligands' water molecules and peripheral pyridyl nitrogen atoms in both the ground and excited states, have been clarified through the measurements of UV-vis, fluorescence, 1H NMR, and dynamic fluorescence decay behaviour. The oxidation potentials in the Pourbaix diagram and spin densities by DFT calculation of the one-electron oxidized form of each nine species have predicted that the fully deprotonated species ([SnTPyP(O-)2]2-) and the singly deprotonated one ([SnTPyP(OH)(O-)]-) serve as the most favourable MCs for visible light-induced two-electron water oxidation when they are adsorbed on TiO2 for H2 formation or SnO2 for Z-scheme CO2 reduction in the molecular catalyst sensitized system of artificial photosynthesis.