Single-Atom based Metal-Organic Framework Photocatalysts for Solar-Fuel Generation.

The growing demand for fossil fuels and subsequent CO2 emissions prompted a search for alternate sources of energy and a reduction in CO2. Photocatalysis driven by solar light has been found as a potential research area to tackle both these problems. In this direction, SAC@MOF (Single-atom loaded MOFs) photocatalysis is an emerging field and a promising technology. The unique properties of single-atom catalysts (SACs), such as high catalytic activity and selectivity, are leveraged in these systems. Photocatalysis, focusing on the utilization of Metal-Organic Frameworks (MOFs) as platforms for creating single-atom catalysts (SACs) characterized by metal single-atoms (SAs) as their active sites, are noted for their unparalleled atomic efficiency, precisely defined active sites, and superior photocatalytic performance. The synergy between MOFs and SAs in photocatalytic systems is meticulously examined, highlighting how they collectively enhance photocatalytic efficiency. This review examines SAC@MOF development and applications in environmental and energy sectors, focusing on synthesis and stabilization methods for SACs on MOFs and also characterization techniques vital for understanding these catalysts. The potential of SAC@MOF in CO2 Photoreduction and Photocatalytic H2 evolution is highlighted, emphasizing its role in green energy technologies and advances in materials science and Photocatalysis.

Atomically Contacted Cs3Bi2Br9 QDs@UiO-66 Composite for Photocatalytic CO2 Reduction.

Metal halide perovskite quantum dots (QDs) are widely studied in the field of photocatalytic CO2 due to their strong light absorption and long carrier migration length. However, it can not exhibit high catalytic performance because of the radiative recombination and the lack of effective catalytic sites. Metal organic frameworks (MOFs) encapsulated QDs can not only solve the aforementioned problems, but also maintain their own unique characteristics with ultra-high specific surfaces area and abundant metal sites. In this work, lead-free bismuth-based halide perovskite QDs are encapsulated into Zr-based MOF (UiO-66), which combines the advantages with high power conversion efficiency of QDs and the high surface area and porosity of UiO-66. In addition, benefiting from the close contact between the Cs3Bi2Br9 QDs and the UiO-66 enables the photogenerated electrons in the QDs to be rapidly transferred to the MOF. As a result, the Cs3Bi2Br9@UiO-66 composite exhibits a higher yield for photocatalytic CO2 reduction than that of the prepared large-sized composite of Cs3Bi2Br9 and UiO-66.

In-Plane Palladium and Interplanar Copper Dual Single-Atom Catalyst in Bulk-Like Carbon Nitride for Cascade CO2 Photoreduction.

Dual single-atom catalysts (DSACs) are promising for breaking the scaling relationships and ensuring synergistic effects compared with conventional single-atom catalysts (SACs). Nevertheless, precise synthesis and optimization of DSACs with specific locations and functions remain challenging. Herein, dual single-atoms are specifically incorporated into the layer-stacked bulk-like carbon nitride, featuring in-plane three-coordinated Pd and interplanar four-coordinated Cu (Pd1-Cu1/b-CN) atomic sites, from both experimental results and DFT simulations. Using femtosecond time-resolved transient absorption (fs-TA) spectroscopy, it is found that the in-plane Pd features a charge decay lifetime of 95.6 ps which is much longer than that of the interplanar Cu (3.07 ps). This finding indicates that the in-plane Pd can provide electrons for the reaction as the catalytically active site in both structurally and dynamically favorable manners. Such a well-defined bi-functional cascade system ensures a 3.47-fold increase in CO yield compared to that of bulk-like CN (b-CN), while also exceeding the effects of single Pd1/b-CN and Cu1/b-CN sites. Furthermore, DFT calculations reveal that the inherent transformation from s-p coupling to d-p hybridization between the Pd site and CO2 molecule occurs during the initial CO2 adsorption and hydrogenation processes and stimulates the preferred CO2-to-CO reaction pathway.

Single-Atom Heterogeneous Catalysts: Human- and AI-Driven Platform for Augmented Designs, Analytics and Reality-Enabled Manufacturing.

Heterogeneous catalysts with targeted functionality can be designed with atomic precision, but it is challenging to retain the structure and performance upon the scaled-up manufacturing. Particularly challenging is to ensure the "atomic economy", where every catalytic site is most gainfully utilized. Given the emerging synergistic integration of human- and artificial intelligence (AI)-driven augmented designs (AD), augmented analytics (AA), and augmented reality manufacturing (AM) platforms, this minireview focuses on single-atom heterogeneous catalysts (SAHCs) and examines the current status, challenges, and future perspectives of translating atomic-level structural precision and data-driven discovery to next-generation industrial manufacturing. We critically examine the atomistic insights into structure-driven SAHCs functionality and discuss the opportunities and challenges on the way towards the synergistic human-AI collaborative data-driven platform capable of monitoring, analyzing, manufacturing, and retaining the atomic-scale structure and functions. Enhanced by the atomic-level AD, AA, and AM, evolving from the current high-throughput capabilities and digital materials manufacturing acceleration, this synergistic human-AI platform is promising to enable atom-efficient and atomically precise heterogeneous catalyst production.

Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two-dimensional Hybrid Perovskite Photocatalysts.

Two-dimensional organic-inorganic hybrid perovskites ( OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron-hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4- octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non-overlapping,which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. DFT calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.

Effect of Functional Group Modifications on the Photocatalytic Performance of g-C3 N4.

In recent years, photocatalysis has received increasing attention in alleviating energy scarcity and environmental treatment, and graphite carbon nitride (g-C3 N4 ) is used as an ideal photocatalyst. However, it still remains numerous challenges to obtain the desirable photocatalytic performance of intrinsic g-C3 N4 . Functional group functionalization, formed by introducing functional groups into the bulk structure, is one of the common modification techniques to modulate the carrier dynamics and increases the number of active sites, offering new opportunities to break the limits for structure-to-performance relationship of g-C3 N4 . Nevertheless, the general overview of the advance of functional group modification of g-C3 N4 is less reported yet. In order to better understand the structure-to-performance relationship at the molecular level, a review of the latest development of functional group modification is urgently needed. In this review, the functional group modification of g-C3 N4 in terms of structures, properties, and photocatalytic activity is mainly focused, as well as their mechanism of reaction from the molecular level insights is explained. Second, the recent progress of the application of introducing functional groups in g-C3 N4 is introduced and examples are given. Finally, the difficulties and challenges are presented, and based on this, an outlook on the future research development direction is shown.

Functionalized MOF-Based Photocatalysts for CO2 Reduction.

Metal-organic frameworks (MOFs) materials have become a research forefront in the field of photocatalytic CO2 reduction attributed to their ultra-high specific surface area, adjustable structure, and abundant catalytic active sites. Particularly, MOFs can be facilely tuned to match CO2 photoreduction by utilizing post-modification of metal nodes, functionalization of organic linkers, and combination with other active materials. Herein, the recent advances in the construction strategy of MOF-based photocatalysts materials for CO2 reduction are highlighted. Some systematic modification strategies on MOF-based photocatalysts are also discussed, such as modification of metal sites and organic ligands, construction of heterojunction, introduction of single/dual-atom, and strain engineering. Finally, the future development directions of MOF-based photocatalysts in the field of CO2 reduction are presented.

Identification of the Active Sites on Metallic MoO2-x Nano-Sea-Urchin for Atmospheric CO2 Photoreduction Under UV, Visible, and Near-Infrared Light Illumination.

We report an oxygen vacancy (Vo )-rich metallic MoO2-x nano-sea-urchin with partially occupied band, which exhibits super CO2 (even directly from the air) photoreduction performance under UV, visible and near-infrared (NIR) light illumination. The Vo -rich MoO2-x nano-sea-urchin displays a CH4 evolution rate of 12.2 and 5.8 µmol gcatalyst -1 h-1 under full spectrum and NIR light illumination in concentrated CO2 , which is ca. 7- and 10-fold higher than the Vo -poor MoO2-x , respectively. More interestingly, the as-developed Vo -rich MoO2-x nano-sea-urchin can even reduce CO2 directly from the air with a CO evolution rate of 6.5 µmol gcatalyst -1 h-1 under NIR light illumination. Experiments together with theoretical calculations demonstrate that the oxygen vacancy in MoO2-x can facilitate CO2 adsorption/activation to generate *COOH as well as the subsequent protonation of *CO towards the formation of CH4 because of the formation of a highly stable Mo-C-O-Mo intermediate.

Highly Strained Bi-MOF on Bismuth Oxyhalide Support with Tailored Intermediate Adsorption/Desorption Capability for Robust CO2 Photoreduction.

Herein, using as-designed surface-mounted Bismuth-based metal-organic framework (Bi-MOF) on two-dimensional BiOBr support, as an operable platform for site-specific strain engineering to tailor the intermediate adsorption/desorption capability in CO2 photocatalytic conversion is proposed. Giant compressive strain up to 7.85 % is successfully induced on the surface-mounted Bi-MOF revealed by HRTEM images and geometric phase analysis as well as in situ Raman characterization, which largely downshifts the p band center of Bi nodes and intensifies their unsaturated state. In-depth explorations are put onto p-p (Bi 6p and CO2 /CO 2p) orbital hybridization. Taking the adsorption process as an example, the 1π and 7σ frontier molecule orbitals of CO2 2p for both the strain-free and strained models shift downwards the Fermi level, indicative of fast adsorption of CO2 . Meanwhile, strain engineering further induces new non-degenerate orbital overlapping near 1π and intensified overlapping of 7σ orbitals, stimulating the fast activation of absorbed CO2 molecules.

Highly Efficient Photocatalytic Reduction of CO2 to CO by In Situ Formation of a Hybrid Catalytic System Based on Molecular Iron Quaterpyridine Covalently Linked to Carbon Nitride.

Efficient and selective photocatalytic CO2 reduction was obtained within a hybrid system that is formed in situ via a Schiff base condensation between a molecular iron quaterpyridine complex bearing an aldehyde function and carbon nitride. Irradiation (blue LED) of an CH3 CN solution containing 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), triethylamine (TEA), Feqpy-BA (qpy-BA=4-([2,2':6',2'':6'',2'''-quaterpyridin]-4-yl)benzaldehyde) and C3 N4 resulted in CO evolution with a turnover number of 2554 and 95 % selectivity. This hybrid catalytic system unlocks covalent linkage of molecular catalysts with semiconductor photosensitizers via Schiff base reaction for high-efficiency photocatalytic reduction of CO2 , opening a pathway for diverse photocatalysis.

Carbon-Graphitic Carbon Nitride Hybrids for Heterogeneous Photocatalysis.

Polymeric graphitic carbon nitride (g-C3 N4 ) and various carbon materials have experienced a renaissance as viable alternates in photocatalysis due to their captivating metal-free features, favorable photoelectric properties, and economic adaptabilities. Although numerous efforts have focused on the integration of both materials with optimized photocatalytic performance in recent years, the direct parameters for this emerging enhancement are not fully summarized yet. Fully understanding the synergistic effects between g-C3 N4 and carbon materials on photocatalytic action is vital to further development of metal-free semiconductors in future studies. Here, recent advances of carbon/g-C3 N4 hybrids on various photocatalytic applications are reviewed. The dominant governing factors by inducing carbon into g-C3 N4 photocatalysts with involving photocatalytic mechanism are highlighted. Five typical carbon-induced enhancement effects are mainly discussed here, i.e., local electric modification, band structure tailoring, multiple charge carrier activation, chemical group functionalization, and abundant surface-modified engineering. Photocatalytic performance of carbon-induced g-C3 N4 photocatalysts for addressing directly both the renewable energy storage and environmental remediation is also summarized. Finally, perspectives and ongoing challenges encountered in the development of metal-free carbon-induced g-C3 N4 photocatalysts are presented.

Single Ni Atoms Anchored on Porous Few-Layer g-C3 N4 for Photocatalytic CO2 Reduction: The Role of Edge Confinement.

It is greatly intriguing yet remains challenging to construct single-atomic photocatalysts with stable surface free energy, favorable for well-defined atomic coordination and photocatalytic carrier mobility during the photoredox process. Herein, an unsaturated edge confinement strategy is defined by coordinating single-atomic-site Ni on the bottom-up synthesized porous few-layer g-C3 N4 (namely, Ni5 -CN) via a self-limiting method. This Ni5 -CN system with a few isolated Ni clusters distributed on the edge of g-C3 N4 is beneficial to immobilize the nonedged single-atomic-site Ni species, thus achieving a high single-atomic active site density. Remarkably, the Ni5 -CN system exhibits comparably high photocatalytic activity for CO2 reduction, giving the CO generation rate of 8.6 µmol g-1 h-1 under visible-light illumination, which is 7.8 times that of pure porous few-layer g-C3 N4 (namely, CN, 1.1 µmol g-1 h-1 ). X-ray absorption spectrometric analysis unveils that the cationic coordination environment of single-atomic-site Ni center, which is formed by Ni-N doping-intercalation the first coordination shell, motivates the superiority in synergistic N-Ni-N connection and interfacial carrier transfer. The photocatalytic mechanistic prediction confirms that the introduced unsaturated Ni-N coordination favorably binds with CO2 , and enhances the rate-determining step of intermediates for CO generation.

Transition-Metal-Ion (Fe, Co, Cr, Mn, Etc.) Doping of TiO2 Nanotubes: A General Approach.

Transition-metal (TM)-ion-doped TiO2 materials are of great importance for photocatalysis- and photoelectrochemical (PEC)-related applications. We introduced a facile, low-cost, and scalable doping method of TM ions (Cr, Co, Cu, Fe, Mn, etc.) into TiO2 nanotubes (NTs), while maintaining their high-ordered tubular structures (with ∼120 nm outside diameter). Both crystallization and doping processes were simultaneously accomplished in aqueous solution at a temperature as low as ∼90 °C, and the fastest doping process could be accomplished in 30 min for Fe doping. Besides, the surface areas of the doped TiO2 NTs were increased to 129.0 m2/g, and their absorption ranges could be expanded from 380 to >500 nm. This study shed light on a facile method for doping TM ions that is extendable to other semiconductors in the field of PEC water splitting and could improve their efficiencies as well.

Magnetite/Iron Foil as an Effective and Nonfiltration Catalyst for Heterogeneous Fenton-like Reactions under Neutral Conditions.

A magnetite/iron foil (MIF) composite was synthesized as a heterogeneous Fenton-like catalyst. The MIF catalyst effectively degraded Rhodamine B under neutral conditions (degradation efficiency = 86%), avoiding the procedure of pH adjustment. The MIF catalyst could be conveniently recycled without filtration, and the advantages of the stability and reusability of a MIF catalyst made it promising in practical wastewater treatment.

Semiconductor terahertz modulator arrays: the size and edge effect.

A terahertz spatial modulator is the critical component for active terahertz imaging using compressive sensing. Here small silicon pieces were put in arrays on flexible polymer substrate to fabricate semiconductor terahertz spatial modulators. By doing this, the inter-diffusion of photo-generated charge carriers is prevented for better resolution, and flexibility is achieved. Since the size of silicon is comparable to the wavelength of the terahertz wave, and the dielectric properties of the gap are very different from silicon, the optical modulation of each element is very different from the large silicon. In this Letter, the terahertz wave interaction and optical modulation of the small silicon are systematically studied by time domain spectroscopy. Notably, a strong resonance-like absorption peak was observed in a transmittance spectrum for the small silicon due to the size and edge effect. The spatial modulation of the terahertz wave was also compared between the silicon array and the large silicon samples.

Fabrication of Heterostructured Metal Oxide/TiO2 Nanotube Arrays Prepared via Thermal Decomposition and Crystallization.

Heterostructured TiO2 materials are of great importance in electronic and photochemical related applications. We report herein a simple, low-cost, and scalable fabrication of metal oxides heterostructured TiO2 nanotube arrays (NTAs) through a combined strategy of thermal decomposition and crystallization. Various M xO y/TiO2 heterostructured films (M = Zn, Ce, Cu, Cr...) were obtained by using TiO2 NTAs as "nano-containers" as well as "nano-reactors", while using M(CH3COO) x solutions as the precursors. SEM, XRD, EDS results demonstrated that Cu2O/TiO2 NTAs, ZnO/TiO2 NTAs, Cr2O3/TiO2 NTAs, and CeO2/TiO2 NTAs were successfully fabricated. Photocatalytic results revealed that the heterostructured M xO y/TiO2 films could either enhance the UV photocatalytic activities or enable the visible light photocatalytic activities of the TiO2 NTAs. This study provides a facile general approach to prepare M xO y/TiO2 NTAs films, which could be very useful for environmental and energy areas.

Graphene-Based Photocatalysts for Solar-Fuel Generation.

The production of solar fuel through photocatalytic water splitting and CO2 reduction using photocatalysts has attracted considerable attention owing to the global energy shortage and growing environmental problems. During the past few years, many studies have demonstrated that graphene can markedly enhance the efficiency of photocatalysts for solar-fuel generation because of its unique 2D conjugated structure and electronic properties. Herein we summarize the recent advances in the application of graphene-based photocatalysts for solar-fuel production, including CO2 reduction to hydrocarbon fuel and water splitting to H2. A brief overview of the fundamental principles for splitting of water and reduction of CO2 is given. The different roles of graphene in these graphene-based photocatalysts for improving photocatalytic performance are discussed. Finally, the perspectives on the challenges and opportunities for future research in this promising area are also presented.

Advances and challenges in the modification of photoelectrode materials for photoelectrocatalytic water splitting.

With the increasing consumption of fossil fuels, the development of clean and renewable alternative fuels has become a top priority. Hydrogen (H2) is an ideal primary clean energy source for its extremely high gravimetric energy density, carbon-free combustion, and abundant natural resources. Photoelectrocatalytic (PEC) water splitting is among the most promising approaches for converting sunlight and water into H2. However, the cost-effectiveness and the overall solar to hydrogen conversion efficiency of PEC water splitting are still big challenges. In the past few decades, several studies have been devoted to this technology, and it is essential to develop economical photoelectrocatalysts with high conversion efficiency. Therefore, there is an urgent need for a comprehensive and updated review of recent advances in the design, manufacture, and modification of efficient PEC water splitting systems. This review first starts with the basic mechanism of photoelectrochemical water splitting. Then the problems in PEC water splitting are discussed, and the methods of photoelectrode modulation such as nanostructure fabrication, doping engineering, surface modification, and heterojunction construction are introduced. Finally, the critical challenges and future trends/perspectives in the PEC water splitting are discussed.

Toward Functionality and Deactivation of Metal-Single-Atom in Heterogeneous Photocatalysts.

Single-atom heterogeneous catalysts (SAHCs) provide an enticing platform for understanding catalyst structure-property-performance relationships. The 100% atom utilization and adjustable local coordination configurations make it easy to probe reaction mechanisms at the atomic level. However, the progressive deactivation of metal-single-atom (MSA) with high surface energy leads to frequent limitations on their commercial viability. This review focuses on the atomistic-sensitive reactivity and atomistic-progressive deactivation of MSA to provide a unifying framework for specific functionality and potential deactivation drivers of MSA, thereby bridging function, purpose-modification structure-performance insights with the atomistic-progressive deactivation for sustainable structure-property-performance accessibility. The dominant functionalization of atomically precise MSA acting on properties and reactivity encompassing precise photocatalytic reactions is first systematically explored. Afterward, a detailed analysis of various deactivation modes of MSA and strategies to enhance their durability is presented, providing valuable insights into the design of SAHCs with deactivation-resistant stability. Finally, the remaining challenges and future perspectives of SAHCs toward industrialization, anticipating shedding some light on the next stage of atom-economic chemical/energy transformations are presented.

Graphene-based semiconductor photocatalysts.

Graphene, a single layer of graphite, possesses a unique two-dimensional structure, high conductivity, superior electron mobility and extremely high specific surface area, and can be produced on a large scale at low cost. Thus, it has been regarded as an important component for making various functional composite materials. Especially, graphene-based semiconductor photocatalysts have attracted extensive attention because of their usefulness in environmental and energy applications. This critical review summarizes the recent progress in the design and fabrication of graphene-based semiconductor photocatalysts via various strategies including in situ growth, solution mixing, hydrothermal and/or solvothermal methods. Furthermore, the photocatalytic properties of the resulting graphene-based composite systems are also discussed in relation to the environmental and energy applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation and photocatalytic disinfection. This critical review ends with a summary and some perspectives on the challenges and new directions in this emerging area of research (158 references).