Modulation of active center distance of hybrid perovskite for boosting photocatalytic reduction of carbon dioxide to ethylene.

Solar-driven photocatalytic CO2 reduction is an energy-efficient and sustainable strategy to mitigate CO2 levels in the atmosphere. However, efficient and selective conversion of CO2 into multi-carbon products, like C2H4, remains a great challenge due to slow multi-electron-proton transfer and sluggish C-C coupling. Herein, a two-dimensional thin-layered hybrid perovskite is fabricated through filling of oxygen into iodine vacancy in pristine DMASnI3 (DMA = dimethylammonium). The rational-designed DMASnI3(O) induces shrinkage of active sites distance and facilitates dimerization of C-C coupling of intermediates. Upon simulated solar irradiation, the DMASnI3(O) photocatalyst achieves a high selectivity of 74.5%, corresponding to an impressive electron selectivity of 94.6%, for CO2 to C2H4 conversion and an effective C2H4 yield of 11.2 µmol g-1 h-1. In addition, the DMASnI3(O) inherits excellent water stability and implements long-term photocatalytic CO2 reduction to C2H4 in a water medium. This work establishes a unique paradigm to convert CO2 to C2+ hydrocarbons in a perovskite-based photocatalytic system.

Interface-confined intermediate phase in TiO2 enables efficient photocatalysis.

As a prototypical photocatalyst, TiO[Formula: see text] has been extensively studied. An interesting yet puzzling experimental fact was that P25-a mixture of anatase and rutile TiO[Formula: see text]-outperforms the individual phases; the origin of this mysterious fact, however, remains elusive. Employing rigorous first-principles calculations, here we uncover a metastable intermediate structure (MIS), which is formed due to confinement at the anatase/rutile interface. The MIS has a high conduction-band minimum level and thus substantially enhances the overpotential of the hydrogen evolution reaction. Also, the corresponding band alignment at the interface leads to efficient separation of electrons and holes. The interfacial confinement additionally creates a wide distribution of the band gap in the vicinity of the interface, which in turn improves optical absorption. These factors all contribute to the enhanced photocatalytic efficiency in P25. Our insights provide a rationale to the puzzling superior photocatalytic performance of P25 and enable a strategy to achieve highly efficient photocatalysis via interface engineering.

A hybrid photocatalytic system enables direct glucose utilization for methanogenesis.

Integration of methanogenic archaea with photocatalysts presents a sustainable solution for solar-driven methanogenesis. However, maximizing CH4 conversion efficiency remains challenging due to the intrinsic energy conservation and strictly restricted substrates of methanogenic archaea. Here, we report a solar-driven biotic-abiotic hybrid (biohybrid) system by incorporating cadmium sulfide (CdS) nanoparticles with a rationally designed methanogenic archaeon Methanosarcina acetivorans C2A, in which the glucose synergist protein and glucose kinase, an energy-efficient route for glucose transport and phosphorylation from Zymomonas mobilis, were implemented to facilitate nonnative substrate glucose for methanogenesis. We demonstrate that the photo-excited electrons facilitate membrane-bound electron transport chain, thereby augmenting the Na+ and H+ ion gradients across membrane to enhance adenosine triphosphate (ATP) synthesis. Additionally, this biohybrid system promotes the metabolism of pyruvate to acetyl coenzyme A (AcCoA) and inhibits the flow of AcCoA to the tricarboxylic acid (TCA) cycle, resulting in a 1.26-fold augmentation in CH4 production from glucose-derived carbon. Our results provide a unique strategy for enhancing methanogenesis through rational biohybrid design and reprogramming, which gives a promising avenue for sustainably manufacturing value-added chemicals.

Enriching surface-ordered defects on WO3 for photocatalytic CO2-to-CH4 conversion by water.

Defect engineering has been widely applied in semiconductors to improve photocatalytic properties by altering the surface structures. This study is about the transformation of inactive WO3 nanosheets to a highly effective CO2-to-CH4 conversion photocatalyst by introducing surface-ordered defects in abundance. The nonstoichiometric WO3-x samples were examined by using aberration-corrected electron microscopy. Results unveil abundant surface-ordered terminations derived from the periodic {013} stacking faults with a defect density of 20.2%. The {002} surface-ordered line defects are the active sites for fixation CO2, transforming the inactive WO3 nanosheets into a highly active catalyst (CH4: O2 = 8.2: 16.7 µmol h-1). We believe that the formation of the W-O-C-W-O species is a critical step in the catalytic pathways. This work provides an atomic-level comprehension of the structural defects of catalysts for activating small molecules.

Quantifying the ultrafast and steady-state molecular reduction potential of a plasmonic photocatalyst.

Plasmonic materials are promising photocatalysts as they are well suited to convert light into hot carriers and heat. Hot electron transfer is suggested as the driving force in many plasmon-driven reactions. However, to date, there are no direct molecular measures of the rate and yield of plasmon-to-molecule electron transfer or energy of these electrons on the timescale of plasmon decay. Here, we use ultrafast and spectroelectrochemical surface-enhanced Raman spectroscopy to quantify electron transfer from a plasmonic substrate to adsorbed methyl viologen molecules. We observe a reduction yield of 2.4 to 3.5% on the picosecond timescale, with plasmon-induced potentials ranging from [Formula: see text]3.1 to [Formula: see text]4.5 mV. Excitingly, some of these reduced species are stabilized and persist for tens of minutes. This work provides concrete metrics toward optimizing material-molecule interactions for efficient plasmon-driven photocatalysis.

Synergy of crystallinity modulation and intercalation engineering in carbon nitride for boosted H2O2 photosynthesis.

Photosynthesis of hydrogen peroxide (H2O2) by selective oxygen reduction is a green and cost-effective alternative to the energy-intensive anthraquinone process. Although inexpensive polymeric graphitic carbon nitride (g-C3N4) exhibits the ability to produce H2O2, its disordered and amorphous structure leads to a high recombination rate of photogenerated carriers and hinders charge transfer between layers. Herein, we predict that stacked polymeric g-C3N4 with ion intercalation (K+ and I-) can improve carrier separation and transfer by multiscale computational simulations. The electronic structures of g-C3N4 were tailored and modified by intercalating K+ and I- into the layer-by-layer structures. Guided by the computational predictions, we achieved efficient solar-driven H2O2 production by employing this facile and ion-intercalated crystalline g-C3N4. An H2O2 production rate of 13.1 mM g-1 h-1 and an apparent quantum yield of 23.6% at 400 nm were obtained. The synergistic effects of crystallinity regulation and dual interstitial doping engineering triggered the formation of new light absorption centers, the establishment of rapid charge diffusion channels, and the enhancement of two-electron oxygen reduction characteristics. This work sheds light on the dual tuning of crystallinity and electronic structure and broadens the design principles of organic-conjugated polymer photocatalysts for environmental remediation and energy conservation.

The optimized Fenton-like activity of Fe single-atom sites by Fe atomic clusters-mediated electronic configuration modulation.

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO2@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N4 active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO5- oxidation and SO5·- desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating 1O2. Subsequently, the hVB+ can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly-enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).

Superexchange-induced Pt-O-Ti3+ site on single photocatalyst for efficient H2 production with organics degradation in wastewater.

Efficient photocatalytic H2 production from wastewater instead of pure water is a dual solution to the environmental and energy crisis, but due to the rapid recombination of photoinduced charge in the photocatalyst and inevitable electron depletion caused by organic pollutants, a significant challenge of dual-functional photocatalysis (simultaneous oxidative and reductive reactions) in single catalyst is designing spatial separation path for photogenerated charges at atomic level. Here, we designed a Pt-doped BaTiO3 single catalyst with oxygen vacancies (BTPOv) that features Pt-O-Ti3+ short charge separation site, which enables excellent H2 production performance (1519 µmol·g-1·h-1) while oxidizing moxifloxacin (k = 0.048 min-1), almost 43 and 98 times than that of pristine BaTiO3 (35 µmol·g-1·h-1 and k = 0.00049 min-1). The efficient charge separation path is demonstrated that the oxygen vacancies extract photoinduced charge from photocatalyst to catalytic surface, and the adjacent Ti3+ defects allow rapid migration of electrons to Pt atoms through the superexchange effect for H* adsorption and reduction, while the holes will be confined in Ti3+ defects for oxidation of moxifloxacin. Impressively, the BTPOv shows an exceptional atomic economy and potential for practical applications, a best H2 production TOF (370.4 h-1) among the recent reported dual-functional photocatalysts and exhibiting excellent H2 production activity in multiple types of wastewaters.

Shewanella oneidensis MR-1 respires CdSe quantum dots for photocatalytic hydrogen evolution.

Living bio-nano systems for artificial photosynthesis are of growing interest. Typically, these systems use photoinduced charge transfer to provide electrons for microbial metabolic processes, yielding a biosynthetic solar fuel. Here, we demonstrate an entirely different approach to constructing a living bio-nano system, in which electrogenic bacteria respire semiconductor nanoparticles to support nanoparticle photocatalysis. Semiconductor nanocrystals are highly active and robust photocatalysts for hydrogen (H2) evolution, but their use is hindered by the oxidative side of the reaction. In this system, Shewanella oneidensis MR-1 provides electrons to a CdSe nanocrystalline photocatalyst, enabling visible light-driven H2 production. Unlike microbial electrolysis cells, this system requires no external potential. Illuminating this system at 530 nm yields continuous H2 generation for 168 h, which can be lengthened further by replenishing bacterial nutrients.

Triggering photocatalytic performance of La2CoxMn2-xO6 via heat activation.

The La-based perovskite (LaBO3) exhibits excellent optical properties. However, its valence band (VB) potential is not sufficiently positive to reach the oxidation potential required for the cleavage of chemical bonds (such as benzylic C-H), limiting its application in photocatalysis. Herein, we report the unconventional effects of heat activation on the reduction of the dissociation energy of benzylic C-H and aqueous H-O, thereby triggering the photocatalytic activity of La2CoxMn2-xO6 perovskites. Additionally, we demonstrate that photocatalysis is the main contributor to substrate conversion in the selective oxidation of toluene and reduction of CO2. Particularly, La2Co1.5Mn0.5O6 shows excellent performance with a product yield of 550.00 mmol gcat-1 and a toluene conversion of 22,866.67 µmol gcat-1 h-1. To the best of our knowledge, this is the highest reported product yield for the selective oxidation of benzylic C-H bond of toluene. Our findings provide insight into the specific role of heat activation in photocatalysis, which is crucial for breaking and overcoming the VB barrier to realize challenging reactions.

Aqueous Titania Interfaces.

Water-metal oxide interfaces are central to many phenomena and applications, ranging from material corrosion and dissolution to photoelectrochemistry and bioengineering. In particular, the discovery of photocatalytic water splitting on TiO2 has motivated intensive studies of water-TiO2 interfaces for decades. So far, a broad understanding of the interaction of water vapor with several TiO2 surfaces has been obtained. However, much less is known about liquid water-TiO2 interfaces, which are more relevant to many practical applications. Probing these complex systems at the molecular level is experimentally challenging and is sometimes possible only through computational studies. This review summarizes recent advances in the atomistic understanding, mostly through computational simulations, of the structure and dynamics of interfacial water on TiO2 surfaces. The main focus is on the nature, molecular or dissociated, of water in direct contact with low-index defect-free crystalline surfaces. The hydroxyls resulting from water dissociation are essential in the photooxidation of water and critically affect the surface chemistry of TiO2.

Small molecule photocatalysis enables drug target identification via energy transfer.

Over half of new therapeutic approaches fail in clinical trials due to a lack of target validation. As such, the development of new methods to improve and accelerate the identification of cellular targets, broadly known as target ID, remains a fundamental goal in drug discovery. While advances in sequencing and mass spectrometry technologies have revolutionized drug target ID in recent decades, the corresponding chemical-based approaches have not changed in over 50 y. Consigned to outdated stoichiometric activation modes, modern target ID campaigns are regularly confounded by poor signal-to-noise resulting from limited receptor occupancy and low crosslinking yields, especially when targeting low abundance membrane proteins or multiple protein target engagement. Here, we describe a broadly general platform for photocatalytic small molecule target ID, which is founded upon the catalytic amplification of target-tag crosslinking through the continuous generation of high-energy carbene intermediates via visible light-mediated Dexter energy transfer. By decoupling the reactive warhead tag from the small molecule ligand, catalytic signal amplification results in unprecedented levels of target enrichment, enabling the quantitative target and off target ID of several drugs including (+)-JQ1, paclitaxel (Taxol), dasatinib (Sprycel), as well as two G-protein-coupled receptors-ADORA2A and GPR40.

Broadband and strong visible-light-absorbing cuprous sensitizers for boosting photosynthesis.

Rational construction of broadband and strong visible-light-absorbing (BSVLA) earth-abundant complexes is of great importance for efficient and sustainable solar energy utilization. Herein, we explore a universal Cu(I) center to couple with multiple strong visible-light-absorbing antennas to break the energy level limitations of the current noble-metal complexes, resulting in the BSVLA nonprecious complex (Cu-3). Systematic investigations demonstrate that double "ping-pong" energy-transfer processes in Cu-3 involving resonance energy transfer and Dexter mechanism enable a BSVLA between 430 and 620 nm and an antenna-localized long-lived triplet state for efficient intermolecular electron/energy transfer. Impressively, Cu-3 exhibited an outstanding performance for both energy- and electron-transfer reactions. Pseudo-first-order rate constant of photooxidation of 1,5-dihydroxynaphthalene with Cu-3 can achieve a record value of 190.8 × 10-3 min-1 among the molecular catalytic systems, over 30 times higher than that with a noble-metal photosensitizer (PS) [Ru(bpy)3]2+. These findings pave the way to develop BSVLA earth-abundant PSs for boosting photosynthesis.

Spontaneous exciton dissociation in organic photocatalyst under ambient conditions for highly efficient synthesis of hydrogen peroxide.

SignificanceHydrogen peroxide is a highly competitive ready-to-use product for solar energy transformation. Nevertheless, the contemporary photosynthetic systems are not efficient enough, due to severe charge recombination caused by high activation energy and binding energy of the exciton. Herein, we achieve spontaneous exciton dissociation at room temperature. Moreover, the photosynthesis of H2O2 reaches between 9,366 and 12,324 µmol·g-1 from 9 AM to 4 PM in ambient conditions, that is, sunlight irradiation, real water including fresh water and seawater, room temperature, and open air. The ultrahigh photocatalytic efficiency in ambient conditions allows the solar-to-chemical conversion in a real cost-effective and sustainable way, which represents an important step toward real applications.

Mass Transport Limitations in Plasmonic Photocatalysis.

The interpretation of mechanisms governing hot carrier reactivity on metallic nanostructures is critical, yet elusive, for advancing plasmonic photocatalysis. In this work, we explored the influence of the diffusion of molecules on the hot carrier extraction rate at the solid-liquid interface, which is of fundamental interest for increasing the efficiency of photodevices. Through a spatially defined scanning photoelectrochemical microscopy investigation, we identified a diffusion-controlled regime hindering the plasmon-driven photochemical activity of metallic nanostructures. Using low-power monochromatic illumination (<2 W cm-2), we unveiled the hidden influence of mass transport on the quantum efficiency of plasmonic photocatalysts. The availability of molecules at the solid-liquid interface directly limits the extraction of hot holes, according to their nature and energy, at the reactive spots in Au nanoislands on an ultrathin TiO2 substrate. An intriguing question arises: does the mass transport enhancement caused by thermal effects unlock the reactivity of nonthermal carriers under steady state?

Interior Exciton Extraction by Spatial-Controlled Iodine Doping in BiOBr Photocatalysts.

Extracting interior photoinduced species to the surface before their recombination is of great importance in pursuing high-efficiency semiconductor-based photocatalysis. Traditional strategies toward charge-carrier extraction, mostly relying on the construction of an electric field gradient, would be invalid toward the neutral-exciton counterpart in low-dimensional systems. In this work, by taking bismuth oxybromide (BiOBr) as an example, we manipulate interior exciton extraction to the surface by implementing iodine doping at the edges of BiOBr plates. Spatial- and time-resolved spectroscopic analyses verified the accumulation of excitons and charge carriers at the edges of iodine-doped BiOBr (BiOBr-I) plates. This phenomenon could be associated with interior exciton extraction, driven by an energy-level gradient between interior and edge exciton states, and the following exciton dissociation processes. As such, BiOBr-I shows remarkable performance in photocatalytic C-H fluorination, mediated by both energy- and charge-transfer processes. This work uncovers the importance of spatial regulation of excitonic properties in low-dimensional semiconductor-based photocatalysis.

A Quasi-Bound States in the Continuum Dielectric Metasurface-Based Antenna-Reactor Photocatalyst.

Metasurfaces are a class of two-dimensional artificial resonators, creating new opportunities for strong light-matter interactions. One type of nonradiative optical metasurface that enables substantial light concentration is based on quasi-Bound States in the Continuum (quasi-BIC). Here we report the design and fabrication of a quasi-BIC dielectric metasurface that serves as an optical frequency antenna for photocatalysis. By depositing Ni nanoparticle reactors onto the metasurface, we create an antenna-reactor photocatalyst, where the virtually lossless metasurface funnels light to drive a chemical reaction. This quasi-BIC-Ni antenna-reactor drives H2 dissociation under resonant illumination, showing strong polarization, wavelength, and optical power dependencies. Both E-field-induced electronic and photothermal heating effects drive the reaction, supported by load-dependent reactivity studies and our theoretical model. This study unlocks new opportunities for photocatalysis that employ dielectric metasurfaces for light harvesting in an antenna-reactor format.

Modularization of Regional Electronic Structure over Defect-Rich CeO2 Rods for Enhancing Photogenerated Charge Transfer and CO2 Activation.

Oxygen vacancy (OV) engineering has been widely applied in different types of metal oxide-based photocatalytic reactions. Our study has shown that the redistributed OVs resulting from voids in CeO2 rods lead to significant differences in the band structure in space. The flat energy band within the highly crystallized bulk region hinders the recombination of photogenerated carrier pairs during the transfer process. The downward curved energy band in the surface region enhances the activation of the absorbents. Therefore, the localization of the band structure through crystal structure regionalization renders V-CeO2 capable of achieving efficient utilization of photogenerated carriers. Practically, the V-CeO2 rod shows a remarkable turnover number of 190.58 µmol g-1 h-1 in CO2 photoreduction, which is ∼9.4 times higher than that of D-CeO2 (20.46 µmol g-1 h-1). The designed modularization structure in our work is expected to provide important inspiration and guidance in coordinating the kinetic behavior of carriers in OV defect-rich photocatalysts.

Tuning Dynamic Structural Evolution of Bi24O31Cl10 for Enhancing Piezo-Photocatalytic Nitrogen Oxidation to Nitrate.

Direct nitrogen oxidation into nitrate under ambient conditions presents a promising strategy for harsh and multistep industrial processes. However, the dynamic structural evolution of active sites in surface reactions constitutes a highly intricate endeavor and remains in its nascent stage. Here, we constructed a Bi24O31Cl10 material with moiré superlattice structure (BCMS) for direct piezo-photocatalytic oxidation of nitrogen into nitrate. Excitingly, BCMS achieved excellent nitric acid production (15.44 mg g-1 h-1) under light and pressure conditions. Detailed experimental results show that the unique structure extracts the local strain tensor from the constricting Bi-Bi bond and Bi-O bond for internal structural reconstruction, which promotes the formation of electron and reactive molecule vortexes to facilitate charge transfer as well as N2 and O2 adsorption. Ultimately, these initiatives strengthen electron exchange between the superoxide radical and nitrogen as well as the binding strength of multiple intermediates, which swayingly adjusts the reaction path and energy barriers.

Defect-Induced All-Solid-State Frustrated Lewis Pair on Metal-Organic Monolayer Accelerating Photocatalytic CO2 Reduction with H2O Vapor.

Understanding the structure-performance relationships of a frustrated Lewis pair (FLP) at the atomic level is key to yielding high efficiency in activating chemically "inert" molecules into value-added products. A sound strategy was developed herein through incorporating oxygen defects into a Zr-based metal-organic layer (Zr-MOL-D) and employing Lewis basic proximal surface hydroxyls for the in situ formation of solid heterogeneous FLP (Zr4-δ-VO-Zr-OH). Zr-MOL-D exhibits a superior CO2 to CO conversion rate of 49.4 µmol g-1 h-1 in water vapor without any sacrificing agent or photosensitizer, which is about 12 times higher than that of pure MOL (Zr-MOL-P), with extreme stability even after being placed for half a year. Theoretical and experimental results reveal that the introduction of FLP converts the process of the crucial intermediate COOH* from an endothermic reaction to an exothermic spontaneous reaction. This work is expected to provide new prospects for developing efficient MOL-based photocatalysts in FLP chemistry through a sound defect-engineering strategy.