[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

Metal nanoparticles stabilized on a support material catalyse many major industrial reactions. Metal-support interactions in these nanomaterials can have a substantial influence on the catalysis, making metal-support interaction modulation one of the few tools able to enhance catalytic performance. This topic has received much attention in recent years, however, a systematic rationalization of the field is lacking due to the great diversity in catalysts, reactions and modification strategies. In this review, we cover and categorize the recent progress in metal-support interaction tuning strategies to enhance catalytic performance for various reactions. Furthermore, we quantify the productivity enhancements resulting from metal-support interaction control that have been achieved in C1 chemistry in recent years. Our analysis shows that up to fifteen-fold productivity enhancement has been achieved, and that metal-support interaction is most impactful for metal nanoparticles smaller than four nanometres. These findings demonstrate the importance of metal-support interaction to improve performance in catalysis. Methods to control the performance of heterogeneous catalysts are extremely relevant to the success of industrial processes. This review provides a rationalization of the effects that metal support interactions have on the reactivity of different catalytic systems, emphasizing strategies to tune such effects.

Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity

Developing highly active and low-cost electrocatalysts with superior durability for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is a grand challenge to produce hydrogen by electrolysis of water. Here, we report on a facile and scalable approach to fabricate highly efficient three-dimensional (3D) bulk catalysts of core–shell nanostructures, in which few-layer NiFe layered double hydroxide (LDH) nanosheets are grown on Cu nanowire cores supported on Cu foams, toward overall water splitting. Remarkably, benefiting from the 3D hierarchical nanoarchitecture with large surface areas, fast electron transport, and open-channels for effective gas release, the resulting 3D self-standing catalysts exhibit outstanding OER activity as well as excellent HER performance in an alkaline medium. Using them as bifunctional catalysts for overall water splitting, a current density of 10 mA cm−2 was achieved at a voltage of 1.54 V, and 100 mA cm−2 at 1.69 V with excellent durability, which is much better than the benchmark of IrO2(+)//Pt(−) electrodes. Our 3D core–shell electrocatalysts significantly advance the research towards large-scale practical water electrolysis.

Cu nanowires shelled with NiFe layered double hydroxide nanosheets as bifunctional electrocatalysts for overall water splitting

In recent years, heterogeneous photocatalysis has received much research interest because of its powerful potential applications in tackling many important energy and environmental challenges at a global level in an economically sustainable manner. Due to their unique optical, electrical, and physicochemical properties, various 2D graphene nanosheets-supported semiconductor composite photocatalysts have been widely constructed and applied in different photocatalytic fields. In this review, fundamental mechanisms of heterogeneous photocatalysis, including thermodynamic and kinetics requirements, are first systematically summarized. Then, the photocatalysis-related properties of graphene and its derivatives, and design rules and synthesis methods of graphene-based composites are highlighted. Importantly, different design strategies, including doping and sensitization of semiconductors by graphene, improving electrical conductivity of graphene, increasing eloectrocatalytic active sites on graphene, strengthening interface coupling between semiconductors and graphene, fabricating micro/nano architectures, constructing multi-junction nanocomposites, enhancing photostability of semiconductors, and utilizing the synergistic effect of various modification strategies, are thoroughly summarized. The important applications including photocatalytic pollutant degradation, H2 production, and CO2 reduction are also addressed. Through reviewing the significant advances on this topic, it may provide new opportunities for designing highly efficient 2D graphene-based photocatalysts for various applications in photocatalysis and other fields, such as solar cells, thermal catalysis, separation, and purification.

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Graphene in Photocatalysis: A Review

Hydrogen (H2) production via photocatalytic water splitting is one of the most promising technologies for clean solar energy conversion to emerge in recent decades. The achievement of energy production from water splitting would mean that we could use water as a fuel for future energy need. Among the various photocatalytic materials, titanium dioxide (TiO2) is the dominant and most widely studied because of its exceptional physico-chemical characteristics. Surface decoration of metal/non-metal on TiO2 nanoparticles is an outstanding technique to revamp its electronic properties and enrich the H2 production efficiency. Metal dopants play a vital role in separation of electron-hole pairs on the TiO2 surface during UV/visible/simulated solar light irradiation. In this paper, the basic principles, photocatalytic-reactor design, kinetics, key findings, and the mechanism of metal-doped TiO2 are comprehensively reviewed. We found that Langmuir-Hinshelwood kinetic model is commonly employed by the researchers to demonstrate the rate of H2 production. Copper (Cu), gold (Au) and platinum (Pt) are the most widely studied dopants for TiO2, owing to their superior work function. The metal dopants can amplify the H2 production efficiency of TiO2 through Schottky barrier formation, surface plasmon resonance (SPR), generation of gap states by interaction with TiO2 VB states. The recent advances and important consequences of 2D materials, perovskites, and other novel photocatalysts for H2 generation have also been reviewed.

Photocatalytic hydrogen production using metal doped TiO2: A review of recent advances

Electrochemical splitting of water is an attractive way to produce hydrogen fuel as a clean and renewable energy source. However, a major challenge is to accelerate the sluggish kinetics of the anodic half-cell reaction where oxygen evolution reaction (OER) takes place. Here, a seamlessly conductive 3D architecture is reported with a carbon-shelled Ni-Co nanowire network as a highly efficient OER electrocatalyst. Highly porous and granular Ni-Co nanowires are first grown on a carbon fiber woven fabric utilizing a cost-effective hydrothermal method and then conductive carbon shell is coated on the Ni-Co nanowires via glucose carbonization and annealing processes. The conductive carbon layer surrounding the nanowires is introduced to provide a continuous pathway for facile electron transport throughout the whole of the integrated 3D catalyst. This 3D hierarchical structure provides several synergistic effects and beneficial functions including a large number of active sites, easy accessibility of water, fast electron transport, rapid release of oxygen gas, enhanced electrochemical durability, and stronger structural integrity, resulting in a remarkable OER activity that delivers an overpotential of 302 mV with a Tafel slope of 43.6 mV dec−1 at a current density of 10 mA cm−2 in an alkaline medium electrolyte (1 m KOH).

Seamlessly Conductive 3D Nanoarchitecture of Core–Shell Ni-Co Nanowire Network for Highly Efficient Oxygen Evolution

The use of hot carriers generated from the decay of localized surface plasmon resonance in noble metal nanoparticles is a promising concept for photocatalysis. Here, we report the enhancement of photocatalytic activity by the flow of hot electrons on TiO2 nanotube arrays decorated with 5-30 nm Au nanoparticles as photoanodes for photoelectrochemical water splitting. This enhanced photocatalytic activity is correlated to the size of the Au nanoparticles, where higher oxygen evolution was observed on the smaller nanoparticles. Conductive atomic force microscopy and ultraviolet photoelectron spectroscopy were used to characterize the Schottky barrier between Au and TiO2, which reveals a reduction in the Schottky barrier with the smaller Au nanoparticles and produces an enhanced transfer of photoinduced hot carriers. This study confirms that the higher photocatalytic activity was indeed driven by the hot electron flux generated from the decay of localized surface plasmon resonance.

Plasmonic hot carrier-driven oxygen evolution reaction on Au nanoparticles/TiO2 nanotube arrays

Hierarchical N-doped TiO2 nanostructured catalysts with micro-, meso-, and macroporosity are synthesized by a facile self-formation route using ammonia and titanium isopropoxide precursor. UV–vis diffuse reflectance spectra confirm the red shift and band gap narrowing due to the doping of N species in the TiO2 nanoporous catalyst. Hierarchical macroporosity with fibrous channel patterning is observed and well preserved even after calcination at 800 °C, indicating thermal stability, whereas micro- and mesoporosity are lost after calcination at 500 °C. The photocatalytic activity of hiearchical N doped TiO2 catalysts loaded with Au is evaluated for H2 production reaction in visible light. The enhanced photocatalytic activity is attributed to the combined synergetic effect of N doping for visible light absorption, micro- and mesoporosity for an increase of effective surface area and light harvestation, and hierarchical macroporous fibrous structure for multiple reflection and effective charge transfer.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/admi.201300018

Enhanced H2 Generation of Au‐Loaded, Nitrogen‐Doped TiO2 Hierarchical Nanostructures under Visible Light

Hot electrons and surface-plasmon-driven chemistry are amongst the most actively studied research subjects because they are deeply associated with energy dissipation and the conversion processes at the surface and interfaces, which are still open questions and key issues in the surface science community. In this topical review, we give an overview of the concept of hot electrons or surface-plasmon-mediated hot electrons generated under various structural schemes (i.e. metals, metal-semiconductor, and metal-insulator-metal) and their role affecting catalytic activity in chemical reactions. We highlight recent studies on the relation between hot electrons and catalytic activity on metallic surfaces. We discuss possible mechanisms for how hot electrons participate in chemical reactions. We also introduce controlled chemistry to describe specific pathways for selectivity control in catalysis on metal nanoparticles.

https://iopscience.iop.org/article/10.1088/0953-8984/28/25/254002/pdf

Song Yi Moon

Papers

Seamlessly Conductive 3D Nanoarchitecture of Core–Shell Ni-Co Nanowire Network for Highly Efficient Oxygen Evolution

Plasmonic hot carrier-driven oxygen evolution reaction on Au nanoparticles/TiO2 nanotube arrays

Enhanced H2 Generation of Au‐Loaded, Nitrogen‐Doped TiO2 Hierarchical Nanostructures under Visible Light

The effect of hot electrons and surface plasmons on heterogeneous catalysis.

Enhanced photocatalytic generation of hydrogen by Pt-deposited nitrogen-doped TiO2 hierarchical nanostructures