Boosting Hydrogen Production of a MOF-based Multicomponent Photocatalyst with Clean Interface via Facile One-pot Electrosynthesis.

Hydrogen production from photocatalysis via the usage of multicomponent photocatalysts represents a promising pathway for carbon peaking and carbon neutrality, owing to their structural advantages in dealing with the three crucial processes in photocatalysis, namely, light harvesting, charge transfer, and surface redox reactions. We demonstrate the fabrication of a MOF-based multicomponent photocatalyst, denoted as semiconductor/MOF/cocatalyst, by a one-pot electrochemical synthetic route. The as-fabricated multicomponent photocatalyst has a clean interface among the components, leading to close connections that contribute to high-quality heterojunction and facilitate photogenerated charge transfer and separation, thereby the efficient hydrogen evolution. The hydrogen production rate of the resultant ZrO2 /Zr-MOF/Pt is 1327 µmol ⋅ g-1 ⋅ h-1 , which is much higher than that of ZrO2 /Zr-MOF (15 µmol ⋅ g-1 ⋅ h-1 ) and pure Zr-MOF (10.1 µmol ⋅ g-1 ⋅ h-1 ), as well as the photodeposited-Pt products ZrO2 /Zr-MOF/PtPD (287 µmol ⋅ g-1 ⋅ h-1 ) and Zr-MOF/PtPD (192 µmol ⋅ g-1 ⋅ h-1 ) obtained by the step-wise synthetic approach. The work gives a good inspiration for the rational design and construction of MOF-based multicomponent photocatalysts through the one-pot electrosynthesis.

Boosting Oxygen Evolution Performance of Nickel-Iron Layered Double Hydroxides by Controlling Oxygen Vacancies and Structural Disorder via n-Butyllithium Treatment.

Nickel-iron-based layered double hydroxides (NiFe-LDHs) are promising catalysts for the oxygen evolution reaction (OER) because of their high activity, availability, and low cost. Defect engineering, particularly the formation of oxygen vacancies, can improve the catalytic activity of NiFe-LDHs. However, the controllable introduction of uniform oxygen vacancies remains challenging. Herein, an n-butyllithium treatment method is developed to tune oxygen vacancy defects and change the degree of amorphization in NiFe-LDHs via deep reduction, followed by partial oxidization at low temperatures. Interestingly, the Ni in the NiFe-LDHs is selectively reduced to the alloy state by n-butyllithium, whereas Fe is not. The different structural transformations of Ni and Fe during the treatment successfully produce an oxygen-defect-rich amorphous/crystalline electrocatalyst. Under optimal conditions, the treated NiFe-LDHs exhibit high OER activity with an overpotential of 223 mV at 10 mA cm-2 (68 mV lower than that of a commercial IrO2 electrocatalyst) and long-term stability. Notably, the n-butyllithium treatment can be applied to other electrocatalysts, such as CoFe-LDHs and IrO2 (treated IrO2 with an overpotential of 197 mV at 10 mA cm-2). This n-butyllithium reduction/partial oxidization treatment constitutes a novel top-down strategy for the controllable modification of metal oxide structures, with various energy-related applications.

Metal-Organic Frameworks for Photocatalysis and Photothermal Catalysis.

To meet the ever-increasing global demand for energy, conversion of solar energy to chemical/thermal energy is very promising. Light-mediated catalysis, including photocatalysis (organic transformations, water splitting, CO2 reduction, etc.) and photothermal catalysis play key roles in solar to chemical/thermal energy conversion via the light-matter interaction. The major challenges in traditional semiconductor photocatalysts include insufficient sunlight utilization, charge carrier recombination, limited exposure of active sites, and particularly the difficulty of understanding the structure-activity relationship. Metal-organic frameworks (MOFs), featuring semiconductor-like behavior, have recently captured broad interest toward photocatalysis and photothermal catalysis because of their well-defined and tailorable porous structures, high surface areas, etc. These advantages are beneficial for rational structural modulation for improved light harvesting and charge separation as well as other effects, greatly helping to address the aforementioned challenges and especially facilitating the establishment of the structure-activity relationship. Therefore, it is increasingly important to summarize this research field and provide in-depth insight into MOF-based photocatalysis and photothermal catalysis to accelerate the future development. In this Account, we have summarized the recent advances in these two directly relevant applications, photocatalysis and photothermal catalysis, mainly focusing on the results in our lab. Given the unique structural features of MOFs, we have put an emphasis on rational material design to optimize the components and performance and to understand related mechanisms behind the enhanced activity. This Account starts by presenting an overview of solar energy conversion by catalysis. We explain why MOFs can be promising photocatalysts and exemplify the semiconductor-like behavior of MOFs. More importantly, we show that MOFs provide a powerful platform to study photocatalysis, in which the involved three key processes, namely, light harvesting, electron-hole separation, and surface redox reactions, can be rationally improved. Meanwhile, the structure-activity relationship and charge separation dynamics are illustrated in this part. In addition, MOFs for photothermal catalysis have been introduced that are based on the photothermal effect of plasmonic metals and/or MOFs, together with light-driven electronic state optimization of active sites, toward enhanced heterogeneous organic reactions. Finally, our brief outlooks on the current challenges and future development of MOF photocatalysis and photothermal catalysis are provided. It is believed that this Account will afford significant understanding and inspirations toward solar energy conversion over MOF-based catalysts.

Integration of Plasmonic Effects and Schottky Junctions into Metal-Organic Framework Composites: Steering Charge Flow for Enhanced Visible-Light Photocatalysis.

A wide range of light absorption and rapid electron-hole separation are desired for efficient photocatalysis. Herein, on the basis of a semiconductor-like metal-organic framework (MOF), a Pt@MOF/Au catalyst with two types of metal-MOF interfaces integrates the surface plasmon resonance excitation of Au nanorods with a Pt-MOF Schottky junction, which not only extends the light absorption of the MOF from the UV to the visible region but also greatly accelerates charge transfer. The spatial separation of Pt and Au particles by the MOF further steers the formation of charge flow and expedites the charge migration. As a result, the Pt@MOF/Au presents an exceptionally high photocatalytic H2 production rate by water splitting under visible light irradiation, far superior to Pt/MOF/Au, MOF/Au and other counterparts with similar Pt or Au contents, highlighting the important role of each component and the Pt location in the catalyst.

Thermally Stable Metal-Organic Framework-Templated Synthesis of Hierarchically Porous Metal Sulfides: Enhanced Photocatalytic Hydrogen Production.

Porous nanostructured materials are demonstrated to be very promising in catalysis due to their well accessible active sites. Thermally stable metal-organic frameworks (MOFs) as hard templates are successfully utilized to afford porous metal oxides and subsequently metal sulfides by a nanocasting method. The resultant metal oxides/sulfides show considerable Brunauer-Emmett-Teller (BET) surface areas, by partially inheriting the pore character of MOF templates. Preliminary investigation on the obtained hierarchically porous CdS for water splitting, as a proof of concept, demonstrates its much higher activity than both corresponding bulk and nanosized counterparts, under visible light irradiation. Given the structural diversity and tailorability of MOFs, such synthetic approach may open an avenue to the synthesis of advanced porous materials for functional applications.

Boosting Photocatalytic Hydrogen Production of a Metal-Organic Framework Decorated with Platinum Nanoparticles: The Platinum Location Matters.

Improving the efficiency of electron-hole separation and charge-carrier utilization plays a central role in photocatalysis. Herein, Pt nanoparticles of ca. 3 nm are incorporated inside or supported on a representative metal-organic framework (MOF), UiO-66-NH2 , denoted as Pt@UiO-66-NH2 and Pt/UiO-66-NH2 , respectively, for photocatalytic hydrogen production via water splitting. Compared with the pristine MOF, both Pt-decorated MOF nanocomposites exhibit significantly improved yet distinctly different hydrogen-production activities, highlighting that the photocatalytic efficiency strongly correlates with the Pt location relative to the MOF. The Pt@UiO-66-NH2 greatly shortens the electron-transport distance, which favors the electron-hole separation and thereby yields much higher efficiency than Pt/UiO-66-NH2 . The involved mechanism has been further unveiled by means of ultrafast transient absorption and photoluminescence spectroscopy.

Impact of Dipole Effect on Perovskite Solar Cells.

Interface modification and bulk doping are two major strategies to improve the photovoltaic performance of perovskite solar cells (PSCs). Dipolar molecules are highly favored due to their unique dipolarity. This review discusses the basic concepts and characteristics of dipoles. In addition, the role of dipoles in PSCs and the corresponding conventional characterization methods for dipoles are introduced. Then, we systematically summarize the latest progress in achieving efficient and stable PSCs in dipole materials at several key interfaces. Finally, we look forward to the future application directions of dipole molecules in PSCs, aiming at providing deep insight and inspiration for developing efficient and stable PSCs.

Influence of F-Containing Materials on Perovskite Solar Cells.

Perovskite solar cells (PSCs) are usually modified and passivated to improve their performance and stability. The interface modification and bulk doping are the two basic strategies. Fluorine (F)-containing materials are highly favored because of their unique hydrophobicity and coordination ability. This review discusses the basic characteristics of F, and the basic principles of improving the photovoltaic performance and stability of PSC devices using F-containing materials. We systematically summarized the latest progress in the application of F-containing materials to achieve efficient and stable PSCs on several key interface layers. It is believed that this work will afford significant understanding and inspirations toward the future application directions of F-containing materials in PSCs, and provide profound insights for the development of efficient and stable PSCs.

Metal-Organic Framework-Based Photocatalysis for Solar Fuel Production.

Metal-organic frameworks (MOFs) represent a novel class of crystalline inorganic-organic hybrid materials with tunable semiconducting behavior. MOFs have potential for application in photocatalysis to produce sustainable solar fuels, owing to their unique structural advantages (such as clarity and modifiability) that can facilitate a deeper understanding of the structure-activity relationship in photocatalysis. This review takes the photocatalytic active sites as a particular perspective, summarizing the progress of MOF-based photocatalysis for solar fuel production; mainly including three categories of solar-chemical conversions, photocatalytic water splitting to hydrogen fuel, photocatalytic carbon dioxide reduction to hydrocarbon fuels, and photocatalytic nitrogen fixation to high-energy fuel carriers such as ammonia. This review focuses on the types of active sites in MOF-based photocatalysts and discusses their enhanced activity based on the well-defined structure of MOFs, offering deep insights into MOF-based photocatalysis.

Phase Interface Regulating on Amorphous/Crystalline Bismuth Catalyst for Boosted Electrocatalytic CO2 Reduction to Formate.

Electroreduction of carbon dioxide into readily collectable and high-value carbon-based fuels is greatly significant to overcome the energy and environmental crises yet challenging in the development of robust and highly efficient electrocatalysts. Herein, a bismuth (Bi) heterophase electrode with enriched amorphous/crystalline interfaces was fabricated via cathodically in situ transformation of Bi-based metal-phenolic complexes (Bi-tannic acid, Bi-TA). Compared with amorphous or crystalline Bi catalyst, the amorphous/crystalline structure Bi leads to significantly enhanced performance for CO2 electroreduction. In a liquid-phase H-type cell, the Faraday efficiency (FE) of formate formation is over 90% in a wide potential range from -0.8 to -1.3 V, demonstrating a high selectivity toward formate. Moreover, in a flow cell, a large current density reaching 600 mA cm-2 can further be rendered for formate production. Theoretical calculations indicate that the amorphous/crystalline Bi heterophase interface exhibits a favorable adsorption of CO2 and lower energy barriers for the rate-determining step compared with the crystalline Bi counterparts, thus accelerating the reaction process. This work paves the way for the rational design of advanced heterointerface catalysts for CO2 reduction.