Photoreduction Research Articles

Cyclic electron flow and Photosystem II-less photosynthesis

Oxygenic photosynthesis is characterised by the cooperation of two photo-driven complexes, Photosystem II (PSII) and Photosystem I (PSI), sequentially linked through a series of redox-coupled intermediates. Divergent evolution has resulted in photosystems exhibiting complementary redox potentials, spanning the range necessary to oxidise water and reduce CO2 within a single system. Catalysing nature’s most oxidising reaction to extract electrons from water is a highly specialised task that limits PSII’s metabolic function. In contrast, potential electron donors in PSI span a range of redox potentials, enabling it to accept electrons from various metabolic processes. This metabolic flexibility of PSI underpins the capacity of photosynthetic organisms to balance energy supply with metabolic demands, which is key for adaptation to environmental changes. Here, we review the phenomenon of ‘PSII-less photosynthesis’ where PSI functions independently of PSII by operating cyclic electron flow using electrons derived from non-photochemical reactions. PSII-less photosynthesis enables supercharged ATP production and is employed, for example, by cyanobacteria’s heterocysts to host nitrogen fixation and by bundle sheath cells of C4 plants to boost CO2 assimilation. We discuss the energetic benefits of this arrangement and the prospects of utilising it to improve the productivity and stress resilience of photosynthetic organisms.

Na+-driven pH regulation by Na+/H+ antiporters promotes photosynthetic efficiency in cyanobacteria.

Photosynthetic organisms have developed mechanisms to regulate light reactions in response to varying light conditions. Photosynthetic electron transport leads to the formation of a ΔpH across the thylakoid membrane, which is crucial for regulating electron transport. However, other pH modulators remain to be identified, particularly in cyanobacteria. In this study, we evaluated the potential involvement of six Na+/H+ antiporters (NhaS1-NhaS6) in control of pH in the cyanobacterium Synechocystis sp. PCC 6803. Synechocystis showed a strong requirement for Na+ at high light intensities, with ΔnhaS1 and ΔnhaS2 strains unable to grow under high light conditions. We analyzed Na+ efflux-driven H+-uptake activities of NhaS1-NhaS6 in inverted membranes of Escherichia coli. Biological fractionation and immunoelectron microscopy revealed that NhaS1 localizes to both the plasma and thylakoid membranes while NhaS2 localizes to the plasma membrane. Measurement of photosynthesis activity indicated that NhaS2 promotes ATP production and electron transport from PQ to P700. Measurements of pH outside of the cells and in the cytoplasm suggested that both NhaS1 and NhaS2 are involved in plasma membrane-mediated light-dependent H+ uptake and cytoplasmic acidification. NhaS1 and NhaS2 were also found to prevent photoinhibition under high light treatment. These results indicate that H+ transport mediated by NhaS1 and NhaS2 plays a role in regulating intracellular pH and maintaining photosynthetic electron transport.

A cluster-nanozyme-coenzyme system mimicking natural photosynthesis for CO2 reduction under intermittent light irradiation

Natural photosynthesis utilizes solar energy to convert water and atmospheric CO2 into carbohydrates through all-weather light/dark reactions based on molecule-based enzymes and coenzymes, inspiring extensive development of artificial photosynthesis. However, development of efficient artificial photosynthetic systems free of noble metals, as well as rational integration of functional units into a single system at the molecular level, remain challenging. Here we report an artificial system, the assembly system of Cu6 cluster and cobalt terpyridine complex, that mimics natural photosynthesis through precise integration of nanozyme complexes and ubiquinone (coenzyme Q) on Cu6 clusters. This biomimetic system efficiently reduces CO2 to CO in light reaction, achieving a production rate of 740.7 μmol·g−1·h−1 with high durability for at least 188 hours. Notably, our system realizes the decoupling of light and dark reactions, utilizing the phenol-evolutive coenzyme Q acting as an electron reservoir. By regulating the stabilizer of coenzyme Q, the dark reaction time can be extended up to 8.5 hours, which fully meets the natural day/night cycle requirements. Our findings advance the molecular design of artificial systems that replicate the comprehensive functions of natural photosynthesis.

Profiling of Key Hub Genes Using a Two-State Weighted Gene Co-Expression Network of 'Jao Khao' Rice under Soil Salinity Stress Based on Time-Series Transcriptome Data.

RNA-sequencing enables the comprehensive detection of gene expression levels at specific time points and facilitates the identification of stress-related genes through co-expression network analysis. Understanding the molecular mechanisms and identifying key genes associated with salt tolerance is crucial for developing rice varieties that can thrive in saline environments, particularly in regions affected by soil salinization. In this study, we conducted an RNA-sequencing-based time-course transcriptome analysis of 'Jao Khao', a salt-tolerant Thai rice variety, grown under normal or saline (160 mM NaCl) soil conditions. Leaf samples were collected at 0, 3, 6, 12, 24, and 48 h. In total, 36 RNA libraries were sequenced. 'Jao Khao' was found to be highly salt-tolerant, as indicated by the non-significant differences in relative water content, cell membrane stability, leaf greenness, and chlorophyll fluorescence over a 9-day period under saline conditions. Plant growth was slightly retarded during days 3-6 but recovered by day 9. Based on time-series transcriptome data, we conducted differential gene expression and weighted gene co-expression network analyses. Through centrality change from normal to salinity network, 111 key hub genes were identified among 1,950 highly variable genes. Enriched genes were involved in ATP-driven transport, light reactions and response to light, ATP synthesis and carbon fixation, disease resistance and proteinase inhibitor activity. These genes were upregulated early during salt stress and RT-qPCR showed that 'Jao Khao' exhibited an early upregulation trend of two important genes in energy metabolism: RuBisCo (LOC_Os10g21268) and ATP synthase (LOC_Os10g21264). Our findings highlight the importance of managing energy requirements in the initial phase of the plant salt-stress response. Therefore, manipulation of the energy metabolism should be the focus in plant resistance breeding and the genes identified in this work can serve as potentially effective candidates.

De-etiolation is Almost Colour Blind: the Study of Photosynthesis Awakening Under Blue and Red Light.

The synthesis and assembly of functioning photosynthetic complexes in chloroplasts developing from etioplasts during the de-etiolation of angiosperm seedlings are imperative for the plant's autotrophic lifestyle. This study compared de-etiolation process under monochromatic red or blue light of equal photon flux density during a 24-hour illumination period of etiolated Arabidopsis seedlings. The aim was to elucidate the impact of these light wavelength on the etioplast-to-chloroplast transformation and the initiation of light-dependent photosynthetic reactions. Both treatments lead to the formation of functional young chloroplasts; however, the etioplast-to-chloroplast transition and the assembly of photosynthetic complexes occurred unevenly, with individual steps tuned by red or blue light. Ultrastructural analysis suggested faster prolamellar bodies disassembly under blue light, while low temperature fluorescence studies indicated a slower transformation of protochlorophyllide to chlorophyllide, and chlorophyll a, under these conditions. Red light further promoted the synthesis of chlorophyll b and LHCII antenna proteins. However, the efficiency of antennae in dissipating excess absorbed energy was higher for seedlings de-etiolated under blue light; the maximum quantum yield of the photosystem II reached 0.81 after 24-hour de-etiolation, equivalent to mature plants. Blue light seemed to enhance the development of well-functioning photosystems (I and II) and antennae. These findings are important for gaining a deeper understanding of photoreceptor regulation of de-etiolation and for utilizing selected light regimes to improve crop yield.

Pitfalls in Photochemical and Photoelectrochemical Reduction of CO2 to Energy Products.

The photochemical and photoelectrochemical reduction of CO2 is a promising approach for converting carbon dioxide into valuable chemicals (materials) and fuels. A key issue is ensuring the accuracy of experimental results in CO2 reduction reactions (CO2RRs) because of potential sources of false positives. This paper reports the results of investigations on various factors that may contribute to erroneous attribution of reduced-carbon species, including degradation of carbon species contained in photocatalysts, residual contaminants from synthetic procedures, laboratory glassware, environmental exposure, and the operator. The importance of rigorous experimental protocols, including the use of labeled 13CO2 and blank tests, to identify true CO2 reduction products (CO2RPs) accurately is highlighted. Our experimental data (eventually complemented with or compared to literature data) underline the possible sources of errors and, whenever possible, quantify the false positives with respect to the effective conversion of CO2 in clean conditions. This paper clarifies that the incidence of false positives is higher in the preliminary phase of photo-material development when CO2RPs are in the range of a few 10s of μg gcat-1 h-1, reducing its importance when significant conversions of CO2 are performed reaching 10s of mol gcat-1 h-1. This paper suggests procedures for improving the reliability and reproducibility of CO2RR experiments, thus validating such technologies.

Photocatalysis with Covalent Organic Frameworks.

ConspectusUtilizing light to enable chemical conversions presents a green and sustainable approach to produce fuels and chemicals, and photocatalysis is one of the key chemical technologies that needs to be well developed in this century. Despite continuous progress in the advancement of various photocatalysts based on small inorganic and organic compounds, polymers, and networks, designing and constructing photocatalysts that combine activity, selectivity, and reusability remains a challenging goal. For catalytic activity, the difficulty originates from the complexity of photochemical reactions, where the light-harvesting system, multielectron and multihole-involving processes, and pinpoint mass delivery simultaneously need to be established in the system. For selectivity, the difficulty stems from the elaborate design of catalytic sites and space, especially their orbital energy levels, spatial arrangement, and environment; developing a molecular strategy that enables an overall design and control of these factors of different aspects is necessary yet arduous. For reusability, the difficulty arises from the stability and recyclability of the photocatalysts upon continuous operation under photoredox reaction conditions. How to recover photocatalysts in an energy-saving way to enable their cyclic use while retaining activity and selectivity is at the core of this problem. These bottleneck issues reflect that molecular design of a photocatalyst is not a simple summation of the above requirements, but a systematic scheme that can organically interlock various aspects is needed.To enable such an elaborate design and precise control, a basic requirement of the scaffold for constructing a promising photocatalyst is that its primary and high-order structures should be molecularly predesignable and synthetically controllable. Such a molecular regime has successfully evolved in natural photosynthesis, where light-harvesting chlorophyll antennae and photocatalytic centers are spatially well-organized and energetically well-defined to build ways for exciton migration, photoinduced electron transfer and charge separation, electron and hole flows, and oxidation of water and reduction of carbon dioxide, thereby converting water into oxygen to release ATP and NADPH via the light reaction and carbon dioxide into glucose with ATP and NADPH through the dark reaction. Similarly, a predesignable polymeric scaffold would be promising for integrating these complex photochemical processes to construct photocatalysts.Covalent organic frameworks (COFs) are a class of extended yet polymeric materials that enable the organization of organic units or metallo-organic moieties into well-defined architectures. In principle, COFs are molecularly designable with topology diagrams and synthetically controllable through polymerization reactions, offering an irreplaceable platform for designing and synthesizing photocatalysts. This feature enticed researchers to develop various photocatalysts based on COFs and drove the rapid progress in this field over the past decade. In this Account, we summarize the recent advances in the molecular design and synthetic control of COF photocatalysts, by highlighting the key achievements in developing ways to enable light harvesting, trigger photoinduced electron transfer and charge separation, allow charge carrier transport and mass delivery, control energy level, catalytic space, and environmental engineering, and develop stability and recyclability with an aim to reveal a full picture of this field. By scrutinizing typical photocatalytic reactions, we show the key problems to be addressed for COFs and predict future directions.

Fabrication of efficient interface carrier channels on multidimensional O[sbnd]CQD Decorated CN Heterojunction for tetracycline degradation via peroxymonosulfate activation

Graphite carbon nitride (CN) is recognized as a promising non-metallic semiconductor photocatalyst for its excellent chemical stability and visible light response. However, the high electron-hole recombination rate in CN greatly limits its photocatalytic performance. To circumvent these limitations, it is particularly important to explore an efficient way to promote the migration of carriers in CN. This study innovatively designs a multidimensional heterojunction between organic carbon quantum (OCQD) and CN, which named as OCQD-CN. OCQD acts as an carriers transfer channel, which effectively promotes the separation efficiency of carriers. Meanwhile, the introduction of OCQD further improves light absorption scope as well as light reaction intensity of CN. By adding peroxymonosulfate (PMS) to form an advanced oxidation process, OCQD-CN10 exhibits a prominent tetracycline (TC) degradation capacity up to 89.1 % within 60 min. The photocatalytic degradation performance of OCQD-CN is significantly improved by 2.0 times with the addition of OCQD. The first-order rate constant corresponding of OCQD-CN10 (0.0300 min−1) is also 2.8 times higher than CN (0.0107 min−1). Thereby, this research underscores the potential of OCQD-CN/PMS system in mitigating water pollution and advancing eco-friendly technologies, offering a promising route to address antibiotic contaminants in the environment.

An effector protein of Fusarium graminearum targets chloroplasts and suppresses cyclic photosynthetic electron flow.

Chloroplasts are important photosynthetic organelles that regulate plant immunity, growth, and development. However, the role of fungal secretory proteins in linking the photosystem to the plant immune system remains largely unknown. Our systematic characterization of 17 chloroplast-targeting secreted proteins of Fusarium graminearum indicated that Fg03600 is an important virulence factor. Fg03600 translocation into plant cells and accumulation in chloroplasts depended on its chloroplast transit peptide. Fg03600 interacted with the wheat (Triticum aestivum L.) proton gradient regulation 5-like protein 1 (TaPGRL1), a part of the cyclic photosynthetic electron transport chain, and promoted TaPGRL1 homo-dimerization. Interestingly, TaPGRL1 also interacted with ferredoxin (TaFd), a chloroplast ferredoxin protein that transfers cyclic electrons to TaPGRL1. TaFd competed with Fg03600 for binding to the same region of TaPGRL1. Fg03600 expression in plants decreased cyclic electron flow (CEF) but increased the production of chloroplast-derived reactive oxygen species (ROS). Stably silenced TaPGRL1 impaired resistance to Fusarium head blight (FHB) and disrupted CEF. Overall, Fg03600 acts as a chloroplast-targeting effector to suppress plant CEF and increase photosynthesis-derived ROS for FHB development at the necrotrophic stage by promoting homo-dimeric TaPGRL1 or competing with TaFd for TaPGRL1 binding.

Strength of activation and temporal dynamics of bioluminescent-optogenetics in response to systemic injections of the luciferin

BioLuminescent OptoGenetics (“BL-OG”) is a chemogenetic method that can evoke optogenetic reactions in the brain non-invasively. In BL-OG, an enzyme that catalyzes a light producing reaction (i.e., a luciferase) is tethered to an optogenetic element that is activated in response to bioluminescent light. Bioluminescence is generated by injecting a chemical substrate (luciferin, e.g., h-Coelenterazine; h-CTZ) that is catalyzed by the luciferase. By directly injecting the luciferin into the brain, we show that bioluminescent light is proportional to spiking activity, and this relationship scales as a function of luciferin dosage. Here, we build on these previous observations by characterizing the temporal dynamics and dose response curves of bioluminescence generated by luminopsins (LMOs), a proxy of BL-OG effects, to intravenous (IV) injections of the luciferin. We imaged bioluminescence through a thinned skull of mice running on a wheel, while delivering h-CTZ via the tail vein with different dosage concentrations and injection rates. The data reveal a systematic relationship between strength of bioluminescence and h-CTZ dosage, with higher concentration generating stronger bioluminescence. We also found that bioluminescent activity occurs rapidly (< 60 s after IV injection) regardless of concentration dosage. However, as expected, the onset time of bioluminescence is delayed as the injection rate decreases. Notably, the strength and time decay of bioluminescence is invariant to the injection rate of h-CTZ. Taken together, these data show that BL-OG effects are highly consistent across injection parameters of h-CTZ, highlighting the reliability of BL-OG as a minimally invasive neuromodulation method.

Evolution of Thylakoid Structural Diversity.

Oxygenic photosynthesis evolved billions of years ago, becoming Earth's main source of biologically available carbon and atmospheric oxygen. Since then, phototrophic organisms have diversified from prokaryotic cyanobacteria into several distinct clades of eukaryotic algae and plants through endosymbiosis events. This diversity can be seen in the thylakoid membranes, complex networks of lipids, proteins, and pigments that perform the light-dependent reactions of photosynthesis. In this review, we highlight the structural diversity of thylakoids, following the evolutionary history of phototrophic species. We begin with a molecular inventory of different thylakoid components and then illustrate how these building blocks are integrated to form membrane networks with diverse architectures. We conclude with an outlook on understanding how thylakoids remodel their architecture and molecular organization during dynamic processes such as biogenesis, repair, and environmental adaptation.

MRNA localization and thylakoid protein biogenesis in the filamentous heterocyst-forming cyanobacterium Anabaena sp. PCC 7120.

Heterocyst-forming cyanobacteria such as Anabaena (Nostoc) sp. PCC 7120 exhibit extensive remodeling of their thylakoid membranes during heterocyst differentiation. Here we investigate the sites of translation of thylakoid membrane proteins in Anabaena vegetative cells and developing heterocysts, using mRNA fluorescent in situ hybridization (FISH) to detect the location of specific mRNA species. We probed mRNAs encoding reaction center core components and the heterocyst-specific terminal oxidases Cox2 and Cox3. As in unicellular cyanobacteria, the mRNAs encoding membrane-integral thylakoid proteins are concentrated in patches at the inner face of the thylakoid membrane system, adjacent to the central cytoplasm. These patches mark the putative sites of translation and membrane insertion of these proteins. Oxidase activity in mature heterocysts is concentrated in the specialized "honeycomb" regions of the thylakoid membranes close to the cell poles. However, cox2 and cox3 mRNAs remain evenly distributed over the inner face of the thylakoids, implying that oxidase proteins migrate extensively after translation to reach their destination in the honeycomb membranes. The RNA-binding protein RbpG is the closest Anabaena homolog of Rbp3 in the unicellular cyanobacterium Synechocystis sp. PCC 6803, which we previously showed to be crucial for the correct location of photosynthetic mRNAs. An rbpG null mutant shows decreased cellular levels of photosynthetic mRNAs and photosynthetic complexes, coupled with perturbations to thylakoid membrane organization and lower efficiency of the Photosystem II repair cycle. This suggests that the chaperoning of photosynthetic mRNAs by RbpG is important for the correct coordination of thylakoid protein translation and assembly.IMPORTANCECyanobacteria have a complex thylakoid membrane system which is the site of the photosynthetic light reactions as well as most of the respiratory activity in the cell. Protein targeting to the thylakoids and the spatial organization of thylakoid protein biogenesis remain poorly understood. Further complexity is found in some filamentous cyanobacteria that produce heterocysts, specialized nitrogen-fixing cells in which the thylakoid membranes undergo extensive remodeling. Here we probe mRNA locations to reveal thylakoid translation sites in a heterocyst-forming cyanobacterium. We identify an RNA-binding protein important for the correct co-ordination of thylakoid protein translation and assembly, and we demonstrate the effectiveness of mRNA fluorescent in situ hybridization (FISH) as a way to probe cell-specific gene expression in multicellular cyanobacteria.

Portable and Hand-Held Ammonia Gas Sensor Enables Noninvasive Prediagnosis of Helicobacter pylori Infection.

Disease diagnosis of Helicobacter pylori (Hp) through human exhaled breath analysis has attracted considerable attention. However, conventional methods, such as carbon 13 (13C) breath test and infrared spectrometers, are facing the challenge of achieving portability and reliability synchronously. Herein, we report a portable and hand-held Hp analyzer using a bimetallic PtRu@SnO2-based gas sensor for the prediagnosis of Hp infection, which is based on detecting ammonia (NH3) as a potential biomarker in exhaled breath. Owing to the surface functionalization through highly catalytically active bimetallic PtRu nanoparticles (NPs) prepared by a photochemical reduction strategy, the PtRu@SnO2-based sensor exhibits high sensitivity and selectivity toward trace-level (200 ppb) NH3 even at high-humidity surroundings (80% RH). Consequently, the designed portable and hand-held Hp analyzer makes the accurate determination of NH3 at 800 ppb in exhaled breath. The tuning of energy band structure and electrical characteristics and the catalytic modulation of NH3 oxidation by PtRu NPs are proposed to be the reasons behind the enhanced NH3 gas-sensing performance, as confirmed by in situ analysis using an online MKS MultiGas 2030 FTIR gas analyzer. This work paves the way for the prediagnosis of Hp infection using a metal oxide gas sensor.

Orange carbon dot nanomaterial as optical/visual sensing platforms for morin and a biomass booster for plant seedlings

The precise regulation of morin levels in both diet and medicine is essential to evaluate the nutritional quality of food. Furthermore, plant yield is attracting considerable attention in the agricultural and herbal industries. Accordingly, the sensing platforms based on orange S and N co-doped carbon dots (SNCDs) were developed to detect morin through photoluminescence signals in aqueous solutions, solid matrices, and zebrafish. These sensing platforms exhibited excellent selectivity toward morin and possessed good anti-interference abilities, achieving limits of detection with 0.31 and 0.19 μM in the aqueous solution and solid state, respectively. Furthermore, the application of the as-prepared SNCDs at low concentration enhanced plant growth (using soybean seedlings as a model). The biological effects may be attributed to the promotion of light reaction and excess light reaction-induced injury. These findings offer novel insights into potential applications of SNCDs in sustainable agriculture and environmental monitoring.

Extended perturbative approach including Redfield and Förster limits for qualitative analysis of exciton dynamics in any photosynthetic light harvesting and reaction center

According to many reports, the various structures of photosynthetic light-harvesting/reaction-center complexes and their molecular-dynamics simulations necessitate a numerically efficient and quality-conserved theory of excitation energy transfer and exciton relaxation in large pigment systems. Although exciton dynamics depend on various parameters, such as exciton coupling strength, exciton–phonon coupling, site energy values for each pigment, and temperature, classifying the transition mechanism for any Hamiltonian into perturbatively delocalized or localized theories is challenging. In this study, perturbative quantum master equations of a reduced density matrix for any orthogonal transformation similar to the coherent modified Redfield theory are derived. Our approach qualitatively conserves the dynamics of relevant perturbative approximations in each limiting case. As an application, any orthogonal transformation of a relevant system is optimized using the average of the square of interactions between orthogonal state transitions. The numerical results for two pigment systems are compared with the limiting formalisms of the modified Redfield and Förster theory.

Hypertension and its correlation with autonomic nervous system dysfunction, heart rate variability and chronic inflammation

Objective This study investigates the relationship between hypertension, dysregulation of the autonomic nervous system, heart rate variability (HRV), and chronic inflammation. Methods We analysed a cohort of 50 hypertensive patients treated at the affiliated Hospital of Jianghan University. The average systolic and diastolic blood pressures (BPs) in this group were 155.26 and 95.32 mmHg, respectively. A control group of 50 healthy volunteers, undergoing routine physical examinations at the same hospital, was also analysed. Results The average systolic BP of the control group was 115.64 ± 10.27 mmHg, and the average diastolic BP was 75.33 ± 8.25 mmHg. In contrast, the experimental group exhibited an average systolic BP of 155.26 ± 20.13 mmHg and an average diastolic BP of 95.32 ± 12.16 mmHg. Both systolic and diastolic BPs were significantly higher in the hypertensive group (p < 0.05). The experimental group also demonstrated reduced HRV and skin conductance response, alongside increased BP variability (BPV), urinary epinephrine levels and prolonged pupillary light reaction time compared to controls (p < 0.05). Notably, Standard Deviation of Normal to Normal Intervals (SDNN) and Root Mean Square of Successive Differences (RMSSD) values were significantly lower in the experimental group (p < 0.05). Furthermore, levels of inflammatory markers such as CRP, TNF-α, IL-6 and IL-1β were markedly elevated in hypertensive patients (p < 0.05). Negative correlations were observed between systolic and diastolic BP with HRV metrics, while positive correlations were found between BP and BPV as well as urinary adrenaline levels. Conclusions The findings indicate that hypertension is closely associated with autonomic nervous system dysfunction, reduced HRV and increased chronic inflammation. A comprehensive approach to hypertension management should integrate these interrelated physiological and pathological mechanisms, with potential therapeutic interventions targeting autonomic function and inflammatory states.

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)

Efficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare‐earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er‐Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g–1 h–1 and 987.7 μmol g–1 h–1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, X‐ray absorption near edge structural analysis, aberration‐corrected transmission electron microscopy, and in‐situ FT‐IR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and density functional theory calculation elucidate that the variety of electronic states induced by 4f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare‐earth‐based dual SAs photocatalysis approach.

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)

Efficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare‐earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er‐Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g–1 h–1 and 987.7 μmol g–1 h–1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, X‐ray absorption near edge structural analysis, aberration‐corrected transmission electron microscopy, and in‐situ FT‐IR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and density functional theory calculation elucidate that the variety of electronic states induced by 4f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare‐earth‐based dual SAs photocatalysis approach.

Artificial Photosynthetic Cell with Molecular Biomimetic Thylakoid.

The construction of solar-to-chemical conversion system by mimicking the photosynthetic network of the chloroplast holds great promise on efficient solar energy utilization. We developed an artificial photosynthetic cell (APC) based on molecular biomimetic thylakoid (CoTPP-FePy) to split water into hydrogen and oxygen (H2 and O2) at low driving voltage (1.1 V) and neutral condition (pH≈7). The CoTPP-FePy can emulate the light reaction in thylakoids to produce O2 by coupling light harvesting, photocatalysis, and electron/energy storage (FeIII/FeII-Py). Subsequently, a membrane electrode assembly (MEA) were employed to simulate the dark reaction, wherein the proton, electron and energy generated by the light reaction can drive the H2 producing process. By a temporally and spatially coupling of the light and dark reactions, the resulting APC achieved a solar conversion efficiency of 3.1%, exceeding that of natural photosynthetic systems and demonstrating the potential of artificial photosynthesis.

Artificial Photosynthetic Cell with Molecular Biomimetic Thylakoid

The construction of solar‐to‐chemical conversion system by mimicking the photosynthetic network of the chloroplast holds great promise on efficient solar energy utilization. We developed an artificial photosynthetic cell (APC) based on molecular biomimetic thylakoid (CoTPP‐FePy) to split water into hydrogen and oxygen (H2 and O2) at low driving voltage (1.1 V) and neutral condition (pH≈7). The CoTPP‐FePy can emulate the light reaction in thylakoids to produce O2 by coupling light harvesting, photocatalysis, and electron/energy storage (FeIII/FeII‐Py). Subsequently, a membrane electrode assembly (MEA) were employed to simulate the dark reaction, wherein the proton, electron and energy generated by the light reaction can drive the H2 producing process. By a temporally and spatially coupling of the light and dark reactions, the resulting APC achieved a solar conversion efficiency of 3.1%, exceeding that of natural photosynthetic systems and demonstrating the potential of artificial photosynthesis.