[Liu, Chang; Li, Feng; Ma, Lai-Peng; Cheng, Hui-Ming] Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China.;Cheng, HM (reprint author), Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua Rd, Shenyang 110016, Peoples R China;cheng@imr.ac.cn

Advanced Materials for Energy Storage

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal–support interaction, and metal–reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results o...

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

Single-atom catalysis has arguably become the most active new frontier in heterogeneous catalysis. Aided by recent advances in practical synthetic methodologies, characterization techniques and computational modelling, we now have a large number of single-atom catalysts (SACs) that exhibit distinctive performances for a wide variety of chemical reactions. This Perspective summarizes recent experimental and computational efforts aimed at understanding the bonding in SACs and how this relates to catalytic performance. The examples described here illustrate the utility of SACs in a broad scope of industrially important reactions and highlight the advantages these catalysts have over those presently used. SACs have well-defined active centres, such that unique opportunities exist for the rational design of new catalysts with high activities, selectivities and stabilities. Indeed, given a certain practical application, we can often design a suitable SAC; thus, the field has developed very rapidly and afforded promising catalyst leads. Moreover, the control we have over certain SAC structures paves the way for designing base metal catalysts with the activities of noble metal catalysts. It appears that we are entering a new era of heterogeneous catalysis in which we have control over well-dispersed single-atom active sites whose properties we can readily tune. Single-atom catalysts are heterogeneous materials featuring active metals sites atomically dispersed on a surface. This Review describes methods by which we prepare and characterize these materials, as well as how we can tune their catalytic performance in a variety of important reactions.

Heterogeneous single-atom catalysis

Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications

Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoring the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

A series of manganese-cerium oxide catalysts were prepared by co-precipitation method and used for low temperature selective catalytic reduction (SCR) of NO x with ammonia in the presence of excess O 2 . These catalysts were characterized by X-ray diffraction (XRD), surface area measurement and FTIR. The experimental results showed that the best Mn-Ce mixed-oxide catalyst yielded 95% NO conversion at 150 °C at a space velocity of 42,000 h −1 . As the manganese content was increased from 0 to 40% (i.e. the molar ratio of Mn/(Mn+Ce)), NO conversion increased significantly, but decreased at higher manganese contents. The most active catalyst was obtained with a molar Mn/(Mn+Ce) ratio of 0.4. Only N 2 rather than N 2 O was found in the product when the temperature was below 150 °C. At higher temperatures, trace amounts of N 2 O were detected. A mechanistic pathway for this reaction was proposed based on earlier findings and FTIR results obtained in this work. The initial step was the adsorption of NH 3 on Lewis acid sites of catalyst, followed by reaction with nitrite species to produce N 2 and H 2 O. Possible intermediates are proposed and all the intermediates could transform into NH 2 NO, which could further react to produce N 2 and H 2 O.

MnOx-CeO2 mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH3 at low temperatures

Performance and kinetics study for low-temperature SCR of NO with NH3 over MnOx–CeO2 catalyst

The high cost and poor thermal durability of current lean nitrogen oxides (NOx) aftertreatment catalysts are two of the major barriers to widespread adoption of highly fuel-efficient diesel engines. We demonstrated the use of strontium-doped perovskite oxides as efficient platinum substitutes in diesel oxidation (DOC) and lean NOx trap (LNT) catalysts. The lanthanum-based perovskite catalysts coated on monolith substrates showed excellent activities for the NO oxidation reaction, a critical step that demands heavy usage of platinum in a current diesel aftertreatment system. Under realistic conditions, La(1-x)SrxCoO3 catalysts achieved higher NO-to-NO2 conversions than a commercial platinum-based DOC catalyst. Similarly, a La(0.9)Sr(0.1)MnO3-based LNT catalyst achieved NOx reduction performance comparable to that of a commercial platinum-based counterpart. The results show promise for a considerably lower-cost diesel exhaust treatment system.

http://science.sciencemag.org/content/sci/327/5973/1624.full.pdf

Strontium-doped perovskites rival platinum catalysts for treating NOx in simulated diesel exhaust.

A series of catalysts of manganese oxide supported on TiO 2 and iron–manganese oxide supported on TiO 2 with different amounts of manganese and iron were studied for low-temperature selective catalytic reduction (SCR) of NO with ammonia in the presence of excess oxygen. It was found that the addition of iron oxide not only increased the NO conversion and N 2 selectivity but also increased the resistance to H 2 O and SO 2 . The Fe–Mn/TiO 2 catalysts yield high activities and high N 2 product selectivity. The N 2 O product selectivity increased with the amount of MnO x as well as temperature. Crystalline phase of MnO x was present at ≥15% Mn on TiO 2 , and the amount increased with Mn content. In addition, SO 2 and H 2 O decreased the activities only slightly, while such effect was reversible. The Fe–Mn/TiO 2 with Mn/Fe=1 showed the highest activity. The results showed that this catalyst yielded nearly 100% NO conversion at 120 °C at a space velocity of 15,000 h −1 . The effect of oxygen was also studied. Reversible transient behaviors similar to that on other oxide catalysts, including vanadia and chromia, were observed for the Fe–Mn/TiO 2 catalyst.

Gongshin Qi

Papers

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

MnOx-CeO2 mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH3 at low temperatures

Performance and kinetics study for low-temperature SCR of NO with NH3 over MnOx–CeO2 catalyst

Strontium-doped perovskites rival platinum catalysts for treating NOx in simulated diesel exhaust.

Low-temperature selective catalytic reduction of NO with NH3 over iron and manganese oxides supported on titania