Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liquid interfaces with a purpose of establishing correlations of size- and shape-dependent chemical and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a molecular level.
Synthesis of bimetallic nanomaterials with well controlled shape is an important topic in heterogeneous catalysis, low-temperature fuel cell technology, and many other fields. Compared with monometallic counterparts, bimetallic nanocatalysts endow scientists with more opportunities to optimize the catalytic performance by modulating the charge transfer between different metals, local coordination environment, lattice strain and surface element distribution. Considering the current challenges in shape controlled synthesis of bimetallic nanocatalysts, this tutorial review highlights some significant achievements in preparing bimetallic alloy, core-shell and heterostructure nanocrystals with well-defined morphologies, summarizes four general routes and some key factors of the bimetallic shape control scenarios, and provides some general ideas on how to design synthetic strategies to control the shape and exposing facets of bimetallic nanocrystals. The composition and shape dependent catalytic behaviours of bimetallic nanocrystals are reviewed as well.
Most materials and devices typically operate under specific environmental conditions, many of them highly reactive. Heterogeneous catalysts, for example, work under high pressure of reactants or in acidic solutions. The relationship between surface structure and composition of materials during operation and their chemical properties needs to be established in order to understand the mechanisms at work and to enable the design of new and better materials. Although studies of the structure, composition, chemical state, and phase transformation under working conditions are challenging, progress has been made in recent years in the development of new techniques that operate under a variety of realistic environments. With them, new chemistry and new structures of materials that are only present under reaction conditions have been uncovered.
Ceria has recently shown intriguing hydrogenation reactivity in catalyzing alkyne selectively to alkenes. However, the mechanism of the hydrogenation reaction, especially the activation of H, remains experimentally elusive. In this work, we report the first direct spectroscopy evidence for the presence of both surface and bulk Ce-H species upon H dissociation over ceria via in situ inelastic neutron scattering spectroscopy. Combined with in situ ambient-pressure X-ray photoelectron spectroscopy, IR, and Raman spectroscopic studies, the results together point to a heterolytic dissociation mechanism of H over ceria, leading to either homolytic products (surface OHs) on a close-to-stoichiometric ceria surface or heterolytic products (Ce-H and OH) with the presence of induced oxygen vacancies in ceria. The finding of this work has significant implications for understanding catalysis by ceria in both hydrogenation and redox reactions where hydrogen is involved.
It is highly desirable and a great challenge for red light emission of carbon dots under long wavelength excitation. Here, we developed a facile route to synthesize carbon dots with red emission due to the doping effect of S and N elements, borrowing from the concept of the semiconductor. The maximum emission locates at 594 nm under 560 nm excitation. The absolute photoluminescence (PL) quantum yield (QY) is as high as 29% and 22% in ethanol and water, respectively. XPS and FTIR spectra illustrated that there exist -SCN and -COOH groups on the surface of the carbon dots. They endow the carbon dots with high sensitivity for ion detection of Fe. The quenched PL emission of Fe-S,N-CDs can be recovered by adding ascorbic acid to release the -COOH and -SCN group due to Fe formation in the presence of ascorbic acid. High PL QY of red emission is beneficial to application in bioimaging. Doxorubicin was loaded onto carbon dots through π-π stacking to form a theranostic agent. When the CD-Dox was injected into the tumor site, a strong PL emission was observed. The PL intensity indicates the concentration of the theranostic agent. After 7 times injection, both the tumor size and weight clearly decrease. The results demonstrate that the S,N-CDs are a potentially excellent bioimaging component in the theranostic field.
Heterogeneous catalysis is a chemical process performed at a solid-gas or solid-liquid interface. Direct participation of catalyst atoms in this chemical process determines the significance of the surface structure of a catalyst in a fundamental understanding of such a chemical process at a molecular level. High-pressure scanning tunneling microscopy (HP-STM) and environmental transmission electron microscopy (ETEM) have been used to observe catalyst structure in the last few decades. In this review, instrumentation for the two in situ/operando techniques and scientific findings on catalyst structures under reaction conditions and during catalysis are discussed with the following objectives: (1) to present the fundamental aspects of in situ/operando studies of catalysts; (2) to interpret the observed restructurings of catalyst and evolution of catalyst structures; (3) to explore how HP-STM and ETEM can be synergistically used to reveal structural details under reaction conditions and during catalysis; and (4) to discuss the future challenges and prospects of atomic-scale observation of catalysts in understanding of heterogeneous catalysis. This Review focuses on the development of HP-STM and ETEM, the in situ/operando characterizations of catalyst structures with them, and the integration of the two structural analytical techniques for fundamentally understanding catalysis.
Catalytic transformation of CH4 under a mild condition is significant for efficient utilization of shale gas under the circumstance of switching raw materials of chemical industries to shale gas. Here, we report the transformation of CH4 to acetic acid and methanol through coupling of CH4, CO and O2 on single-site Rh1O5 anchored in microporous aluminosilicates in solution at ≤150 °C. The activity of these singly dispersed precious metal sites for production of organic oxygenates can reach about 0.10 acetic acid molecules on a Rh1O5 site per second at 150 °C with a selectivity of ~70% for production of acetic acid. It is higher than the activity of free Rh cations by >1000 times. Computational studies suggest that the first C–H bond of CH4 is activated by Rh1O5 anchored on the wall of micropores of ZSM-5; the formed CH3 then couples with CO and OH, to produce acetic acid over a low activation barrier.
A catalytic site typically consists of one or more atoms of a catalyst surface that arrange into a configuration offering a specific electronic structure for adsorbing or dissociating reactant molecules. The catalytic activity of adjacent bimetallic sites of metallic nanoparticles has been studied previously. An isolated bimetallic site supported on a non-metallic surface could exhibit a distinctly different catalytic performance owing to the cationic state of the singly dispersed bimetallic site and the minimized choices of binding configurations of a reactant molecule compared with continuously packed bimetallic sites. Here we report that isolated Rh 1 Co 3 bimetallic sites exhibit a distinctly different catalytic performance in reduction of nitric oxide with carbon monoxide at low temperature, resulting from strong adsorption of two nitric oxide molecules and a nitrous oxide intermediate on Rh 1 Co 3 sites and following a low-barrier pathway dissociation to dinitrogen and an oxygen atom. This observation suggests a method to develop catalysts with high selectivity.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.