Field Of Artificial Photosynthesis Research Articles

Visible-Light-Driven Reduction of CO2 to CO with Highly Active and Selective Earth-Abundant Metal Porphyrin-Conjugated Organic Polymers.

The field of artificial photosynthesis, which focuses on harnessing solar light for the conversion of CO2 to economically valuable chemical products, remains a captivating area of research. In this study, we developed a series of photocatalysts based on Earth abundant elements (Fe, Co, Ni, Cu, and Zn) incorporated into 2D metalloporphyrin-conjugated organic polymers known as MTBPP-BEPA-COPs. These photocatalysts were utilized for the photoreduction of CO2 employing only H2O as the electron donor, without the need for any sacrificial agents or precious-metal cocatalysts. Remarkably, all of the synthesized MTBPP-BEPA-COPs exhibited an exceptional CO2 photoreduction performance only irradiated by visible light. Particularly, upon optimizing the metal ion coordinated with porphyrin units, ZnTBPP-BEPA-COP outperformed the other MTBPP-BEPA-COPs in terms of photocatalytic activity, achieving an impressive CO reduction yield of 152.18 μmol g-1 after just 4 h of irradiation. The electrostatic potential surfaces calculated by density functional theory suggest the potential involvement of metal centers as binding and catalytic sites for the binding of CO2. The calculated adsorption energy of CO2 with ZnTBPP-BEPA-COP exhibited one of the two smallest values. This may be the reason for the excellent catalytic effect of ZnTBPP-BEPA-COP. Thus, the present study not only demonstrates the potential of porphyrin-based conjugated polymers as highly efficient photocatalysts for CO2 reduction but also offers valuable insights into the rational design of such materials in the future.

Regulating the Transfer of Photogenerated Carriers for Photocatalytic Hydrogen Evolution Coupled with Furfural Synthesis.

How to simultaneously utilize photogenerated electrons and holes still remains a critical challenge in the field of artificial photosynthesis, especially in the process of photocatalytic hydrogen (H2) evolution coupled with biomass oxidation to value-added chemicals. Herein, a series-parallel photocatalyst (Cu NPs/CdS/In2O3) that can intrinsically regulate the transfer of photogenerated carriers is ingeniously designed for photocatalytic H2 evolution synergized with furfural alcohol (FFA) selective oxidation to furfural (FF). Accordingly, the desired H2 and FF evolution rates with near 100% selectivity toward FF are achieved on Cu NPs/CdS/In2O3 in a sealed atmospheric system. Experimental and theoretical analyses confirm that the localized surface plasmon resonance (LSPR) effect induced by Cu NPs accelerates the reduction of protons (H+) to H2 efficiently, while the photogenerated holes from In2O3 preferentially activate the α-C-H bond of FFA adsorbed on Lewis acid sites to generate FF. This work provides a reference for regulating the transfer of photogenerated carriers for H2 evolution coupled with FF synthesis.

Facile construction of MoS2 decorated CdS hybrid heterojunction with enhanced hydrogen generation performance

Promoting the charge separation to improve photocatalytic performance of semiconductor photocatalysts is very important in the field of artificial photosynthesis. Here, a novel MoS2/CdS 2D–2D ultrathin nanosheet heterostructure was fabricated via a one-pot solvothermal route. The obtained 2D–2D MoS2/CdS nanojunction has not only provided large contact areas, but also shortened the charge transport distance, resulting in significantly enhanced photocatalytic H2 evolution property. The composites that were synthesized were examined using X-ray diffraction (XRD), Field emission scanning electron microscope (FESEM), Transmission electron microscope (TEM), UV-vis diffuse reflectance spectra (DRS), Photoluminescence (PL) and X-ray photoelectron spectra (XPS) analysis. By optimizing the 2D MoS2 amounts in the heterojunction, the 5 wt.% 2D/2D MoS2/CdS heterojunction displayed the maximal photocatalytic H2 evolution rate of 4449 μmolh−1g−1 under visible light irradiation in the presence of lactic acid as the sacrificial reagent, which was 6 times higher than that of pristine 2D CdS. Based on the photoelectrochemical and photoluminescence spectra tests, it could be deduced that the charge separation and transfer of 2D/2D MoS2/CdS heterojunction was tremendously improved, and the recombination of photoinduced electron-hole pairs was effectively impeded. Moreover, the 2D MoS2 was used as a cocatalyst to provide the abundant active sites and lower the overpotential for H2 generation reaction. The current work would offer an insight to fabricate the 2D/2D heterojunction photocatalysts for splitting H2O into H2.

Rationalizing In Situ Active Repair in Hydrogen Evolution Photocatalysis via Non‐Invasive Raman Spectroscopy

AbstractCurrently, most photosensitizers and catalysts used in the field of artificial photosynthesis are still based on rare earth metals and should thus be utilized as efficiently and economically as possible. While repair of an inactivated catalyst is a potential mitigation strategy, this remains a challenge. State‐of‐the‐art methods are crucial for characterizing reaction products during photocatalysis and repair, and are currently based on invasive analysis techniques limiting real‐time access to the involved mechanisms. Herein, we use an innovative in situ technique for detecting both initially evolved hydrogen and after active repair via advanced non‐invasive rotational Raman spectroscopy. This facilitates unprecedently accurate monitoring of gaseous reaction products and insight into the mechanism of active repair during light‐driven catalysis enabling the identification of relevant mechanistic details along with innovative repair strategies.

Rationalizing In Situ Active Repair in Hydrogen Evolution Photocatalysis via Non-Invasive Raman Spectroscopy.

Currently, most photosensitizers and catalysts used in the field of artificial photosynthesis are still based on rare earth metals and should thus be utilized as efficiently and economically as possible. While repair of an inactivated catalyst is a potential mitigation strategy, this remains a challenge. State-of-the-art methods are crucial for characterizing reaction products during photocatalysis and repair, and are currently based on invasive analysis techniques limiting real-time access to the involved mechanisms. Herein, we use an innovative in situ technique for detecting both initially evolved hydrogen and after active repair via advanced non-invasive rotational Raman spectroscopy. This facilitates unprecedently accurate monitoring of gaseous reaction products and insight into the mechanism of active repair during light-driven catalysis enabling the identification of relevant mechanistic details along with innovative repair strategies.

Artificial Photosynthesis: Current Advancements and Future Prospects.

Artificial photosynthesis is a technology with immense potential that aims to emulate the natural photosynthetic process. The process of natural photosynthesis involves the conversion of solar energy into chemical energy, which is stored in organic compounds. Catalysis is an essential aspect of artificial photosynthesis, as it facilitates the reactions that convert solar energy into chemical energy. In this review, we aim to provide an extensive overview of recent developments in the field of artificial photosynthesis by catalysis. We will discuss the various catalyst types used in artificial photosynthesis, including homogeneous catalysts, heterogeneous catalysts, and biocatalysts. Additionally, we will explore the different strategies employed to enhance the efficiency and selectivity of catalytic reactions, such as the utilization of nanomaterials, photoelectrochemical cells, and molecular engineering. Lastly, we will examine the challenges and opportunities of this technology as well as its potential applications in areas such as renewable energy, carbon capture and utilization, and sustainable agriculture. This review aims to provide a comprehensive and critical analysis of state-of-the-art methods in artificial photosynthesis by catalysis, as well as to identify key research directions for future advancements in this field.

Functionalized 2D defect g-C3N4 for artificial photosynthesis of H2O2 and synchronizing tetracycline fluorescence detection and degradation

Artificial photosynthesis of H2O2 is a clean production technology, which brings the synergistic effect to photodegradation of pollutants. Inspired by defect engineering, 2D defective carbon nitride (g-C3N4) photocatalyst was obtained via potassium ion assisted synthesis. Defective g-C3N4 is protonated and applied to photosynthesis of H2O2, H2O2 concentration produced reached 477.7 μM, which was approximately 5.27 times that by pristine g-C3N4. Additionally, defective g-C3N4 materials are borrowed to synchronizing tetracycline (TC) fluorescence detection and degradation, suggesting the catalyst existed bifunctional characteristics of TC detection and degradation. Meanwhile, metal impregnation engineering (molybdenum) was borrowed enhancing the electron-trapping ability in local region of defective g-C3N4, which takes advantages to the efficient degradation of TC. Furthermore, optical and electrical properties of photocatalysts were investigated in details by advanced material characterization testing. This work provides potential applications in the field of artificial photosynthesis and pollution degradation.

Photosynthesis of Hydrogen Peroxide Based on g-C3 N4 : The Road of a Cost-Effective Clean Fuel Production.

Emerging artificial photosynthesis promises to offer a competitive means for solar energy conversion and further solves the energy crisis facing the world. Hydrogen peroxide (H2 O2 ), which is considered as a benign oxidant and a prospective liquid fuel, has received worldwide attention in the field of artificial photosynthesis on account of the source materials are just oxygen, water, and sunlight. Graphitic carbon nitride (g-C3 N4 )-based photocatalysts for H2 O2 generation have attracted extensive research interest due to the intrinsic properties of g-C3 N4 . In this review, research processes for H2 O2 generation on the basis of g-C3 N4 , including development, fabrication, merits, and disadvantages, and the state-of-the-art methods to enhance the performance are summarized after a brief introduction and the mechanism analysis of an efficient catalytic system. Also, recent applications of g-C3 N4 -based photocatalysts for H2 O2 production are reviewed, and the significance of active sites and synthetic pathways are highlighted from the view of reducing barriers. Finally, this paper ends with some concluding remarks to reveal the issues and opportunities of g-C3 N4 -based photocatalysts for producing H2 O2 in a high yield.

Manipulating the Reaction Pathway of CO2 Photoreduction via the Microenvironment of a Re Molecular Catalyst

Re molecular complexes incorporated into two metal-organic frameworks were investigated to disclose the host-guest interaction by infrared and 1H nuclear magnetic resonance and to explore the microenvironment around the Re complex by absorption and photoluminescence spectra. ZIF-8 provides a confined space to isolated Re via an electrostatic interaction, while UiO-66 exerts a relaxed space to accessible Re via a coordination interaction. For CO2 two-electron photoreduction to CO, the turnover number of 28.6 in Re@ZIF-8 is 10-fold that of 2.7 in Re@UiO-66. The electron transfer is promoted in Re@ZIF-8 by a local electrostatic field with a cross-space pathway, whereas it is retarded in Re@UiO-66 as the solvation shell surrounding Re. In the following CO2 activation, the charged intermediate species could be stabilized in Re@ZIF-8 by spatial confinement, while Re-triethanolamine adducts prevailed in Re@UiO-66 with the accessibility of the Re complex. This work demonstrates a feasibility of diverting the CO2 activation pathway by the microenvironment of a molecular catalyst in the field of artificial photosynthesis.

Panchromatic Pt/TiO2-Based Photocatalysts Sensitized with Carboxylated Chlorin Dyads for Water Splitting Hydrogen Evolution

Harvesting and converting solar energy into hydrogen production provides a new strategy for the global energy crisis. Since TiO2, the most widely used photocatalyst, absorbs light limited in ultraviolet region, extension of photo-response in visible to near-infrared region by dye-sensitization of TiO2 photocatalysts has attracted more and more attention in the field of artificial photosynthesis. In this work, three chlorophyll(Chl)-related sensitizers were designed to realize panchromatic light-absorption to simulate the charge separation process in natural photosynthetic reaction centers. The dyad sensitizers were synthesized by covalently-linking two different types of chromophore units derived from natural Chls-a/b, and their effects of Pt/TiO2-based photocatalysts for water splitting hydrogen evolution reaction (HER) were investigated. The Pt/TiO2 composite sensitized with Chl-a type dyad showed the best photocatalytic HER performance, and the H2 evolution of 5.4 mmol g-1h-1 was achieved. Electronic absorption, fluorescence emission, and time-resolved photoluminescence spectra as well as photocurrent responses and electrochemical impedance measurements were used to reveal the key factors of dyad sensitizers that influence the performances of Pt/TiO2 based photocatalysts. This work provides insights to explore new organic dye-sensitizers for improving the performance of TiO2-based photocatalysts.

Morphology Matters: 0D/2D WO3 Nanoparticle‐Ruthenium Oxide Nanosheet Composites for Enhanced Photocatalytic Oxygen Evolution Reaction Rates

AbstractIn the field of artificial photosynthesis with semiconductor light harvesters, the default cocatalyst morphologies are isotropic, 0D nanoparticles. Herein, the use of highly anisotropic 2D ruthenium oxide nanosheet (RONS) cocatalysts as an approach to enhance photocatalytic oxygen evolution (OER) rates on commercial WO3 nanoparticles (0D light harvester) is presented. At optimal cocatalyst loadings and identical photocatalysis conditions, WO3 impregnated with RONS (RONS/WO3) shows a fivefold increase in normalized photonic efficiency compared to when it is impregnated with conventional ruthenium oxide (rutile) nanoparticles (RONP/WO3). The superior RONS/WO3 performance is attributed to two special properties of the RONS: i) lower electrochemical water oxidation overpotential for RONS featuring highly active edge sites, and ii) decreased parasitic light absorption on RONS. Evidence is presented that OER photocatalytic performance can be doubled with control of RONS edges and it is shown that compared to WO3 impregnated with RONP, the advantageous optical properties and geometry of RONS decrease the fraction of light absorbed by the cocatalyst, thus reducing the parasitic light absorption on the RONS/WO3 composite. Therefore, the results presented in the current study are expected to promote engineering of cocatalyst morphology as a complementary concept to optimize light harvester‐cocatalyst composites for enhanced photocatalytic efficiency.

Ligand-free CsPbBr3 with calliandra-like nanostructure for efficient artificial photosynthesis

The low-efficiency CO2 uptake capacity and insufficient photogenerated exciton dissociation of current metal halide perovskite (MHP) nanocrystals with end-capping ligands extremely restrict their application in the field of artificial photosynthesis. Herein, we demonstrate that ligand-free CsPbBr3 with calliandra-like nanostructure (LF-CPB CL) can be synthesized easily through a ligand-free seed-assisted dissolution-recrystallization growth process, exhibiting significantly enhanced CO2 uptake capacity. More specifically, the abundant surface bromine (Br) vacancies in ligand-free MHP materials are demonstrated to be beneficial to photogenerated carrier separation. The electron consumption rate of LF-CPB CL for photocatalytic CO2 reduction increases 7 and 20 times over those of traditional ligand-capping CsPbBr3 nanocrystal (L-CPB NC) and bulk CsPbBr3, respectively. Moreover, the absence of ligand hindrance can facilitate the interfacial electronic coupling between LF-CPB CL and tetra(4-carboxyphenyl)porphyrin iron(III) chloride (Fe-TCPP) cocatalyst, bringing forth significantly accelerated interfacial charge separation. The LF-CPB CL/Fe-TCPP exhibits a total electron consumption rate of 145.6 μmol g−1 h−1 for CO2 photoreduction coupled with water oxidation, which is over 14 times higher than that of L-CPB NC/Fe-TCPP.

Enhancement of power conversion efficiency by chlorophyll and carotenoid co-sensitization in the biosolar cells

Photosynthetic pigment-based biosolar cells (BSCs) have attracted much attention over the past few years in the field of artificial photosynthesis. To further improve the power conversion efficiency (PCE) of chlorophyll (Chl)-based bilayer BSCs, co-sensitization effects of three carboxylated chromophores, methyl trans-32-carboxy-pyropheophorbide-a (H2Chl-1), methyl 7-deformyl-7-(trans-carboxyethenyl)-pyropheophorbide-b (H2Chl-2), and β-apo-8′-carotenoic acid (Car) were investigated as H2Chl-1:H2Chl-2, H2Chl-1:Car, and H2Chl-2:Car combinations. The homogeneously co-sensitized mesoporous TiO2 (m-TiO2) layer (TiO2–H2Chl:Car) serves as the photoactive and electron extraction layer, while a Chl-a derivative, zinc methyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (ZnChl) forms J-type self-aggregation film and acts as electron donor layer. The light absorption and electron injection efficiency of the TiO2 sensitized H2Chl-1:Car blends are better than those of other types of co-sensitization after optimizing the blend ratio of each type. The electron absorption spectrum of TiO2–(H2Chl-1:Car) at the best mass ratio of 10:3 (molar ratio of 12:5) showed wider absorption band in 350–450 nm region compared to the spectrum of sole TiO2–(H2Chl-1). The charge transfer resistance was significantly reduced when TiO2–(H2Chl-1:Car) was applied for BSCs. The best PCE of 2.13% was achieved using TiO2–(H2Chl-1:Car = 10:3), which corresponds to 40% increase of PCE compared to the device using TiO2–(H2Chl-1) without Car.

Photocatalytic Systems for CO2 Reduction: Metal-Complex Photocatalysts and Their Hybrids with Photofunctional Solid Materials.

ConspectusPhotocatalytic CO2 reduction is a critical objective in the field of artificial photosynthesis because it can potentially make a total solution for global warming and shortage of energy and carbon resources. We have successfully developed various highly efficient, stable, and selective photocatalytic systems for CO2 reduction using transition metal complexes as both photosensitizers and catalysts. The molecular architectures for constructing selective and efficient photocatalytic systems for CO2 reduction are discussed herein. As a typical example, a mixed system of a ring-shaped Re(I) trinuclear complex as a photosensitizer and fac-[Re(bpy)(CO)3{OC2H4N(C2H4OH)2}] as a catalyst selectively photocatalyzed CO2 reduction to CO with the highest quantum yield of 82% and a turnover number (TON) of over 600. Not only rare and noble metals but also earth abundant ones, such as Mn(I), Cu(I), and Fe(II) can be used as central metal cations. In the case using a Cu(I) dinuclear complex as a photosensitizer and fac-Mn(bpy)(CO)3Br as a catalyst, the total formation quantum yield of CO and HCOOH from CO2 was 57% and TONCO+HCOOH exceeded 1300.Efficient supramolecular photocatalysts for CO2 reduction, in which photosensitizer and catalyst units are connected through a bridging ligand, were developed for removing a diffusion control on collisions between a photosensitizer and a catalyst. Supramolecular photocatalysts, in which [Ru(N∧N)3]2+-type photosensitizer and Re(I) or Ru(II) catalyst units are connected to each other with an alkyl chain, efficiently and selectively photocatalyzed CO2 reduction in solutions. Mechanistic studies using time-resolved IR and electrochemical measurements provided molecular architecture for constructing efficient supramolecular photocatalysts. A Ru(II)–Re(I) supramolecular photocatalyst constructed according to this molecular architecture efficiently photocatalyzed CO2 reduction even when it was fixed on solid materials. Harnessing this property of the supramolecular photocatalysts, two types of hybrid photocatalytic systems were developed, namely, photocatalysts with light-harvesting capabilities and photoelectrochemical systems for CO2 reduction.Introduction of light-harvesting capabilities into molecular photocatalytic systems should be important because the intensity of solar light shone on the earth’s surface is relatively low. Periodic mesoporous organosilica, in which methyl acridone groups are embedded in the silica framework as light harvesters, was combined with a Ru(II)–Re(I) supramolecular photocatalyst with phosphonic acid anchoring groups. In this hybrid, the photons absorbed by approximately 40 methyl acridone groups were transferred to one Ru(II) photosensitizer unit, and then, the photocatalytic CO2 reduction commenced.To use water as an abundant electron donor, we developed hybrid photocatalytic systems combining metal-complex photocatalysts with semiconductor photocatalysts that display high photooxidation powers, in which two photons are sequentially absorbed by the metal-complex photosensitizer and the semiconductor, resulting in both high oxidation and reduction power. Various types of dye-sensitized molecular photocathodes comprising the p-type semiconductor electrodes and the supramolecular photocatalysts were developed. Full photoelectrochemical cells combining these dye-sensitized molecular photocathodes and n-type semiconductor photoanodes achieved CO2 reduction using only visible light as the energy source and water as the reductant. Drastic improvement of dye-sensitized molecular photocathodes is reported.The results presented in this Account clearly indicate that we can construct very efficient, selective, and durable photocatalytic systems constructed with the metal-complex photosensitizers and catalysts. The supramolecular-photocatalyst architecture in which the photosensitizer and the catalyst are connected to each other is useful especially on the surface of solid owing to rapid electron transfer from the photosensitizer to the catalyst. On basis of these findings, we successfully constructed hybrid systems of the supramolecular photocatalysts with photoactive solid materials. These hybridizations can add new functions to the metal-complex photocatalytic systems, such as water oxidation and light harvesting.

Insights into Proton Coupled Electron Transfer in the Field of Artificial Photosynthesis

AbstractArtificial photosynthesis with respect to water splitting is usually divided into water oxidation catalysis (WOC) and the hydrogen evolution reaction (HER). Though in the combined redox dissociation of water into oxygen and hydrogen no protons and electrons occur, both half reactions show photoinduced proton coupled electron transfer (PCET). Regarding a classical approach, photosensitizers (PS) deliver electrons and protons that are accepted by water reduction catalysts (WRC) containing suitable basic atoms like nitrogen working as proton relays. However, the mechanisms of PCET reactions differ, where concerted proton electron transfer (CPET) is an elementary step. In CPET simultaneous electron and proton transfer occurs in the femtoseconds range, being rapid when compared to the periods for coupled vibrations and solvent modes. This has to be distinguished from stepwise electron and proton transfer, leading to underlying thermodynamics of the intermediates. DFT calculations based on X‐ray diffraction (XRD) data help to specify the different reaction pathways. A plethora of experimental procedures are used in order to verify the theoretical predictions. Among them femtosecond pump‐probe spectroscopic measurements play an important role. Furthermore, cyclic voltammetry (CV) has proven to be also a powerful tool. In the case of electrochemical PCET rotating‐disk electrode voltammetry, electrochemical impedance spectroscopy and spectroelectrochemistry complete the experimental tools. In this minireview a selection of examples, where PCET occurs is discussed with respect to possible mechanisms and used methods.

Two‐Dimensional Metal Halide Perovskite Nanosheets for Efficient Photocatalytic CO2 Reduction

Metal halide perovskite (MHP) nanocrystals (NCs) have attained ever‐increasing attention in the field of artificial photosynthesis, due to their desirable strong light‐harvesting capacity and long lifetime of photogenerated carriers. However, the well‐known inherent instability and inferior activity of MHP NCs limit their application foreground in photocatalysis. Herein, a series of 2D MHP nanosheets have been synthesized based on a facile approach at room temperature. These 2D materials are used as photocatalysts for the photocatalysis of CO2 reduction without any organic sacrificial agents, which display significantly improved stability compared to traditional MHP NCs in water‐contained reaction system. More importantly, benefitting from the large proportion of low‐coordinated metal atoms and short carrier diffusion distance, these MHP nanosheets exhibit a remarkably increased performance for photocatalytic CO2 reduction. The judicious modulation of halide component endows the MHP nanosheets with a highest electron consumption rate of 87.8 μmol g−1 h−1 among the reported pure MHP catalysts for photocatalytic CO2 conversion, which is over seven times higher than that of traditional MHP NCs.

High Performance Generation of H2 O2 under Piezophototronic Effect with Multi-Layer In2 S3 Nanosheets Modified by Spherical ZnS and BaTiO3 Nanopiezoelectrics.

Manipulating the separation and transportation of photoexcited charge carriers in photoresponsive semiconductors via the piezoelectric polarization effect is an emerging strategy in the field of artificial photosynthesis. However, existing semiconductor photocatalysts, both with a wide range absorption for visible light and superior piezoelectricity are very scarce, leading to a low reactivity of photocatalysis. Here, a multi-layer In2 S3 nanosheet modified with spherical ZnS and BaTiO3 nanopiezoelectrics (ZnS/In2 S3 /BTO) is reported, generating approximately 378 µm of H2 O2 in 100min (and the concentration is still increasing) under co-irradiation of visible light and ultrasound (piezophotocatalysis) in ethanol-water solution; this concentration is higher compared with two phases piezoelectric heterostructures (i.e., ZnS/BTO, In2 S3 /BTO, and ZnS/In2 S3 ) and pure compounds (i.e., ZnS, In2 S3 , and BTO), and also higher than that of independent piezo- (≈254 µm) and photocatalysis (≈120 µm). Moreover, the concentration of H2 O2 generated on ZnS/In2 S3 /BTO can be as high as approximately 1160 µm in 5 h of piezophotoreaction after experiencing six cycles of visible light concurrent with ultrasound irradiation. The enhancement of H2 O2 yield on ZnS/In2 S3 /BTO in piezophotocatalysis can be attributed to the piezopotential-induced internal electric polarization field promoting the separation of photoexcited charge carriers, thus boosting the rate of surface photoreaction.

Synthesis and Characterization of a Covalent Porphyrin‐Cobalt Diimine‐Dioxime Dyad for Photoelectrochemical H2 Evolution

AbstractThe utilization of solar energy via photoelectrochemical cells (PEC) towards hydrogen (H2) production is a promising approach in the field of artificial photosynthesis. In this work, the synthesis and complete characterization of the first covalently linked porphyrin‐cobalt diimine‐dioxime dyad (ZnP‐Co) is reported. The synthetic procedure that was followed is based on simple and high yielding reactions, without using any noble metal. Photophysical investigation of the dyad revealed sufficient electronic communication between the sensitizer and the catalyst in the excited state. Finally, NiO films were sensitized with ZnP‐Co and the H2‐evolving photoelectrochemical activity of the resulting photocathode was assessed. The modest performances could be rationalized thanks to photolysis and post‐operando characterizations of the system, thus providing some guidelines toward the design of more efficient porphyrin‐based assemblies.

Photocatalysis of a Dinuclear Ru(II)-Re(I) Complex for CO2 Reduction on a Solid Surface.

The development of CO2-reduction photocatalysts is one of the main targets in the field of artificial photosynthesis. Recently, numerous hybrid systems in which supramolecular photocatalysts comprised of a photosensitizer and catalytic-metal-complex units are immobilized on inorganic solid materials, such as semiconductors or mesoporous organosilica, have been reported as CO2-reduction photocatalysts for various functions, including water oxidation and light harvesting. In the present study, we investigated the photocatalytic properties of supramolecular photocatalysts comprised of a Ru(II)-complex photosensitizer and a Re(I)-complex catalyst fixed on the surface of insulating Al2O3 particles: the distance among the supramolecular photocatalyst molecules should be fixed. Visible-light irradiation of the photocatalyst in the presence of an electron donor under a CO2 atmosphere produced CO selectively. Although CO formation was also observed for a 1:1 mixture of mononuclear Ru(II) and Re(I) complexes attached to an Al2O3 surface, the photocatalytic activity was much lower. The activity of the Al2O3-supported photocatalyst was strongly dependent on the adsorption density of the supramolecular moiety, where the initial rate of photocatalytic CO formation was faster at lower density and higher photocatalyst durability was achieved at higher density. One of the main reasons for the former phenomenon is the decreased quenching fraction of the excited state of the photosensitizer unit by the reductant dissolved in the solution phase in the case of higher density. This is due to the self-quenching of the excited photosensitizer unit and steric hindrance between the condensed supramolecular photocatalyst molecules attached to the surface. The higher durability of the more condensed system is caused by intermolecular electron transfer between reduced supramolecular photocatalyst molecules, which accelerates the formation of CO in the photocatalytic CO2 reduction. Coadsorption of a Ru(II) mononuclear complex as a redox photosensitizer could drastically reinforce the photocatalysis of the supramolecular photocatalyst on the surface of the Al2O3 particles: more than 10 times higher turnover number and about 3.4 times higher turnover frequency of CO formation. These investigations provide new architectures for the construction of efficient and durable hybrid photocatalytic systems for CO2 reduction, which are composed of metal-complex photocatalysts and solid materials.

Influence of Surface Ligands on Charge-Carrier Trapping and Relaxation in Water-Soluble CdSe@CdS Nanorods

In this study, the impact of the type of ligand at the surface of colloidal CdSe@CdS dot-in-rod nanostructures on the basic exciton relaxation and charge localization processes is closely examined. These systems have been introduced into the field of artificial photosynthesis as potent photosensitizers in assemblies for light driven hydrogen generation. Following photoinduced exciton generation, electrons can be transferred to catalytic reaction centers while holes localize into the CdSe seed, which can prevent charge recombination and lead to the formation of long-lived charge separation in assemblies containing catalytic reaction centers. These processes are in competition with trapping processes of charges at surface defect sites. The density and type of surface defects strongly depend on the type of ligand used. Here we report on a systematic steady-state and time-resolved spectroscopic investigation of the impact of the type of anchoring group (phosphine oxide, thiols, dithiols, amines) and the bulkiness of the ligand (alkyl chains vs. poly(ethylene glycol) (PEG)) to unravel trapping pathways and localization efficiencies. We show that the introduction of the widely used thiol ligands leads to an increase of hole traps at the surface compared to trioctylphosphine oxide (TOPO) capped rods, which prevent hole localization in the CdSe core. On the other hand, steric restrictions, e.g., in dithiolates or with bulky side chains (PEG), decrease the surface coverage, and increase the density of electron trap states, impacting the recombination dynamics at the ns timescale. The amines in poly(ethylene imine) (PEI) on the other hand can saturate and remove surface traps to a wide extent. Implications for catalysis are discussed.