Sites Of Heterogeneous Catalysts Research Articles

Enhanced tetracycline hydrochloride degradation at near neutral conditions with FeOx modified Bi4TaO8Cl catalyst: Coupling the photocatalytic and Fenton oxidation

The efficient regeneration of Fe2+ active sites in heterogeneous catalysts is of great significance for the photo-Fenton progress. Herein, amorphous FeOx as one efficient cocatalyst was anchored on the Bi4TaO8Cl nanosheets to boost the activation of H2O2 and the separation of photogenerated carriers. The surface-exposed FeOx can produce Fe2+ active sites by extracting the photogenerated electrons from Bi4TaO8Cl. As a result, the redox cycle of Fe3+/Fe2+ was built and the carriers were separated to boost the continuous photo-Fenton degradation. As a result, H2O2 are continuously activated through the cycle of Fe3+/Fe2+. The coupling of photocatalysis and the Fenton reaction enhances the TC-H degradation performance and suppress the loss-activation of iron sites. The optimized FeOx/Bi4TaO8Cl sample exhibited the highest degradation ratio of about 83.5 % in 20 min, which was nearly 4 times that of the pure Bi4TaO8Cl. In addition, the better performance of FeOx/Bi4TaO8Cl catalyst under near-neutral conditions also sheds new insights about the design of efficient photo-Fenton catalysts that can work under mild conditions.

Spatial confinement and erbium-mediated electronic modulation for enhanced 4-nitrophenol destruction through peroxymonosulfate activation

The development of efficient strategies to modulate the electron structure of active sites in heterogeneous catalysts is crucial but remains challenging for enhancing peroxomonosulfate (PMS) activation to degrade organic contaminants. In this study, Co-Er-N-doped carbon black materials are successfully synthesized by pyrolyzing the CB@Er/Co-complex precursor. Er-doping does not enhance the defect level or graphitization degree of the carbon matrix, but rather regulates the electronic structure of Co sites, thereby generating abundant metallic Co species for activating PMS and yield increased reactive oxygen species towards 4-nitrophenol (4-NP) degradation. The optimal Er/Co@NCB-0.6 catalyst exhibits a removal efficiency of 97.9 % in 20 min. Furthermore, this catalyst exhibits broad degradation capabilities against various organic contaminants. Due to the spatial confinement effect from carbon layers, the encapsulated Co nanoparticles in the Er/Co@NCB-0.6 catalyst demonstrate excellent stability and reusability for the reaction. Radical quenching and electron paramagnetic resonance results indicate that the Er/Co@NCB-0.6/PMS system involves radical and non-radical pathways, and 1O2 and SO4•− play essential role in degrading 4-NP. The pollutant is degraded into seventeen intermediates via two plausible pathways. This study provides a valuable rare metal-mediated strategy to regulate the electronic structure of Co-based catalytic materials towards activating PMS in removing persistent organic pollutants.

Nitrogen species from Spirulina platensis derived bio-oil enhance catalytic activity of cobalt catalysts for hydrogenation

High nitrogen content in Spirulina platensis-derived bio-oil is a highly undesirable feature in upgrading of bio-oil to biofuel via hydrodeoxygenation. However, the nitrogen species could be potentially used as dopant for tailoring the catalytic behaviors of metallic sites in heterogeneous catalysts. In this study, the nitrogen species in the bio-oil from hydrothermal carbonization (HTC) of Spirulina platensis was used to modify Co-based catalyst for enhancing their catalytic activity for hydrogenation of o-chloronitrobenzene (o-CNB). The results showed that the introduction of N species not only promoted dispersion of Co particles via formation of Co–N sites, but also generated extra pores and significantly increased H2 uptake. The abundant Co–N sites, high dispersion of Co and higher surface area of N-doped catalyst (CoFeAl–N) jointly contributed to the enhanced catalytic activity for hydrogenation of o-CNB, achieving the yield of 90.3% for o-chloroaniline (o-CA) and lowering the activation energy from 63.0 kJ mol−1 (with N-free CoFeAl catalyst) to 55.1 kJ mol−1. The effectiveness of introducing nitrogen for enhancing catalytic activity for hydrogenation of o-CNB was also confirmed in the experiments for doping Co/Al2O3 (prepared via impregnation) and CoAl (prepared via co-precipitation) catalysts with the Spirulina platensis derived bio-oil.

Polarized metal-metal multiple bonding and reactivity of phosphinoamide-bridged heterobimetallic group IV/cobalt compounds.

Heterobimetallic complexes are studied for their ability to mimic biological systems as well as active sites in heterogeneous catalysts. While specific interest in early/late heterobimetallic systems has fluctuated, they serve as important models to fundamentally understand metal-metal bonding. Specifically, the polarized metal-metal multiple bonds formed in highly reduced early/late heterobimetallic complexes exemplify how each metal modulates the electronic environment and reactivity of the complex as a whole. In this Perspective, we chronicle the development of phosphinoamide-supported group IV/cobalt heterobimetallic complexes. This combination of metals allows access to a low valent Co-I center, which performs a rich variety of bond activation reactions when coupled with the pendent Lewis acidic metal center. Conversely, the low valent late transition metal is also observed to act as an electron reservoir, allowing for redox processes to occur at the d0 group IV metal site. Most of the bond activation reactions carried out by phosphinoamide-bridged M/Co-I (M = Ti, Zr, Hf) complexes are facilitated by cleavage of metal-metal multiple bonds, which serve as readily accessible electron reservoirs. Comparative studies in which both the number of buttressing ligands as well as the identity of the early metal were varied to give a library of heterobimetallic complexes are summarized, providing a thorough understanding of the reactivity of M/Co-I heterobimetallic systems.

Semi-quantitative determination of active sites in heterogeneous catalysts for photo/electrocatalysis

This review focuses on exploring the defect active sites by determining the location and type and semi-quantitative calculation of defect concentrations by a variety of representational methods.

Stepwise assembly of thiacalix[4]arene-protected Ag/Ti bimetallic nanoclusters: accurate identification of catalytic Ag sites in CO2 electroreduction.

The accurate identification of catalytic sites in heterogeneous catalysts poses a significant challenge due to the intricate nature of controlling interfacial chemistry at the molecular level. In this study, we introduce a novel strategy to address this issue by utilizing a thiacalix[4]arene (TC4A)-protected Ti-oxo core as a template for loading Ag1+ ions, leading to the successful synthesis of a unique Ag/Ti bimetallic nanocluster denoted as Ti8Ag8. This nanocluster exhibits multiple surface-exposed Ag sites and possesses a distinctive "core-shell" structure, consisting of a {Ti4@Ag8(TC4A)4} core housing a {Ti2O2@Ag4(TC4A)2} motif and two {Ti@Ag2(TC4A)} motifs. To enable a comprehensive analysis, we also prepared a Ti2Ag4 cluster with the same {Ti2O2@Ag4(TC4A)2} structure found within Ti8Ag8. The structural disparities between Ti8Ag8 and Ti2Ag4 provide an excellent platform for a comparison of catalytic activity at different Ag sites. Remarkably, Ti8Ag8 exhibits exceptional performance in the electroreduction of CO2 (eCO2RR), showcasing a CO faradaic efficiency (FECO) of 92.33% at -0.9 V vs. RHE, surpassing the FECO of Ti2Ag4 (69.87% at -0.9 V vs. RHE) by a significant margin. Through density functional theory (DFT) calculations, we unveil the catalytic mechanism and further discover that Ag active sites located at {Ti@Ag2(TC4A)} possess a higher εd value compared to those at {Ti2O2@Ag4(TC4A)2}, enhancing the stabilization of the *COOH intermediate during the eCO2RR. This study provides valuable insights into the accurate identification of catalytic sites in bimetallic nanoclusters and opens up promising avenues for efficient CO2 reduction catalyst design.

Adsorbate-driven dynamic active sites in stannosilicate zeolites

Elucidating the nature of the active sites in heterogeneous catalysts is fundamental for understanding their reactivity and catalytic performances. Although stannosilicate zeolites have tremendous application potential for catalyzing biomass-related compounds in aqueous media, the detailed local structures and features of the real active sites and their possible structural variations under reaction conditions are poorly understood to date. In this study, a dynamic transformation of framework Sn−O−Si sites to Sn−OH/Si−OH pairs and subsequently a pseudo-Brønsted acid in stannosilicate zeolites upon molecular adsorption, which is analogous to various adsorbates/reactants under working conditions, was identified by solid-state nuclear magnetic resonance (NMR) spectroscopy for the first time, which challenges the widespread assumption that the active center structures remain rigid/stable during the catalytic process. These results provide new comprehensive insights for the fundamental understanding of the dynamic and flexible active centers and involved reaction mechanisms of novel zeolite catalysts with heterometal atoms, such as Sn, Ti, and Zr.

Chiral Frustrated Lewis Pair@Metal‐Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation

AbstractAsymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms of activation by non‐metal sites of heterogeneous catalysts. Herein, as demonstrated by combined computational and experimental studies, we present a general strategy for integrating rationally designed molecular chiral frustrated Lewis pair (CFLP) with porous metal–organic framework (MOF) to construct the catalyst CFLP@MOF that can efficiently promote the asymmetric hydrogenation in a heterogeneous manner, which for the first time extends the concept of chiral frustrated Lewis pair from homogeneous system to heterogeneous catalysis. Significantly, the developed CFLP@MOF, inherits the merits of both homogeneous and heterogeneous catalysts, with high activity/enantio‐selectivity and excellent recyclability/regenerability. Our work not only advances CFLP@MOF as a new platform for heterogeneous asymmetric hydrogenation, but also opens a new avenue for the design and preparation of advanced catalysts for asymmetric catalysis.

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions**

AbstractThis Review provides a summary of the use and the role of coordination complexes as precursors for the generation of heterogeneous catalysts for oxidation reactions of interest for fine chemical synthesis. Specific attention is paid to the comprehension of phenomena explaining the formation of active sites in heterogeneous catalysts. Different families of coordination precursors are considered. For each example, a brief critical description of the synthesis, characterization, and catalytic performance is reported. Special attention is paid to the chemical environment of the first coordination sphere of the active metal centre. The catalysts obtained by heterogenization, grafting, or anchoring of homogeneous catalysts can therefore exhibit enhanced catalytic performance by merging advantages of both homogeneous and heterogeneous systems. The deposition of coordination complexes over a preformed support is indeed a conceptually versatile strategy to design novel catalysts with tuned and controlled properties.

The Control of the Coordination Chemistry for the Genesis of Heterogeneous Catalytically Active Sites in Oxidation Reactions.

This Review provides a summary of the use and the role of coordination complexes as precursors for the generation of heterogeneous catalysts for oxidation reactions of interest for fine chemical synthesis. Specific attention is paid to the comprehension of phenomena explaining the formation of active sites in heterogeneous catalysts. Different families of coordination precursors are considered. For each example, a brief critical description of the synthesis, characterization, and catalytic performance is reported. Special attention is paid to the chemical environment of the first coordination sphere of the active metal centre. The catalysts obtained by heterogenization, grafting, or anchoring of homogeneous catalysts can therefore exhibit enhanced catalytic performance by merging advantages of both homogeneous and heterogeneous systems. The deposition of coordination complexes over a preformed support is indeed a conceptually versatile strategy to design novel catalysts with tuned and controlled properties.

Determining the Three-Dimensional Structures of Silica-Supported Metal Complexes from the Ground Up.

The immobilization of molecularly precise metal complexes to substrates, such as silica, provides an attractive platform for the design of active sites in heterogeneous catalysts. Specific steric and electronic variations of the ligand environment enable the development of structure-activity relationships and the knowledge-driven design of catalysts. At present, however, the three-dimensional environment of the precatalyst, much less the active site, is generally not known for heterogeneous single-site catalysts. We explored the degree to which NMR-based surface-to-complex interatomic distances could be used to solve the three-dimensional structures of three silica-supported metal complexes. The structure solution revealed unexpected features related to the environment around the metal that would be difficult to discern otherwise. This approach appears to be highly robust and, due to its simplicity, is readily applied to most single-site catalysts with little extra effort.

Lewis‐Basic EDTA as a Highly Active Molecular Electrocatalyst for CO2 Reduction to CH4

AbstractThe most active catalysts so far successful in hydrogenation reduction of CO2 are mainly heterogeneous Cu‐based catalysts. The complex coordination environments and multiple active sites in heterogeneous catalysts result in low selectivity of target product, while molecular catalysts with well‐defined active sites and tailorable structures allow mechanism‐based performance optimization. Herein, we firstly report a single ethylenediaminetetraacetic acid (EDTA) molecular‐level immobilized on the surface of carbon nanotube as a catalyst for transferring CO2 to CH4 with an excellent performance. This catalyst exhibits a high Faradaic efficiency of 61.6 % toward CH4, a partial current density of −16.5 mA cm−2 at a potential of −1.3 V versus reversible hydrogen electrode. Density functional theory calculations reveal that the Lewis basic COO− groups in EDTA molecule are the active sites for CO2 reduction reaction (CO2RR). The energy barrier for the generation of CO from *CO intermediate is as high as 0.52 eV, while the further protonation of *CO to *CHO follows an energetic downhill path (−1.57 eV), resulting in the high selectivity of CH4. This work makes it possible to control the product selectivity for CO2RR according to the relationship between the energy barrier of *CO intermediate and molecular structures in the future.

Lewis-Basic EDTA as a Highly Active Molecular Electrocatalyst for CO2 Reduction to CH4.

The most active catalysts so far successful in hydrogenation reduction of CO2 are mainly heterogeneous Cu-based catalysts. The complex coordination environments and multiple active sites in heterogeneous catalysts result in low selectivity of target product, while molecular catalysts with well-defined active sites and tailorable structures allow mechanism-based performance optimization. Herein, we firstly report a single ethylenediaminetetraacetic acid (EDTA) molecular-level immobilized on the surface of carbon nanotube as a catalyst for transferring CO2 to CH4 with an excellent performance. This catalyst exhibits a high Faradaic efficiency of 61.6 % toward CH4 , a partial current density of -16.5 mA cm-2 at a potential of -1.3 V versus reversible hydrogen electrode. Density functional theory calculations reveal that the Lewis basic COO- groups in EDTA molecule are the active sites for CO2 reduction reaction (CO2 RR). The energy barrier for the generation of CO from *CO intermediate is as high as 0.52 eV, while the further protonation of *CO to *CHO follows an energetic downhill path (-1.57 eV), resulting in the high selectivity of CH4 . This work makes it possible to control the product selectivity for CO2 RR according to the relationship between the energy barrier of *CO intermediate and molecular structures in the future.

Tuning the reversible chemisorption of hydroxyl ions to promote the electrocatalysis on ultrathin metal-organic framework nanosheets

Interfacial engineering to alter the configuration of active sites in heterogeneous catalysts is a potential strategy for activity enhancement, but it remains unelucidated for metal-organic frameworks (MOFs). Here, we demonstrate that the surface of two-dimensional Co-based MOF is modified by decorating Ag quantum dots (QDs) simply through in-situ reduction of Ag+ ions. Toward oxygen evolution reaction (OER), it reveals that the catalysis is mediated by the reversible redox of Co sites between Co3+ and Co4+ states coupling with transfer of OH− ions. The decoration of Ag QDs decreases the redox potential of Co sites, and thus effectively decreases the overpotential of OER. The TOFs of Co sites are increased by 77 times to reach 5.4 s−1 at an overpotential of 0.35 V. We attribute the activity enhancement to the tuning of the coupling process between Co sites and OH− ions during the redox of Co sites by Ag QDs decoration based on Pourbaix analysis.

More than little fragments of matter: Electronic and molecular structures of clusters.

Small clusters have captured the imaginations of experimentalists and theorists alike for decades. In addition to providing insight into the evolution of properties between the atomic or molecular limits and the bulk, small clusters have revealed a myriad of fascinating properties that make them interesting in their own right. This perspective reviews how the application of anion photoelectron (PE) spectroscopy, typically coupled with supporting calculations, is particularly well-suited to probing the molecular and electronic structure of small clusters. Clusters provide a powerful platform for the study of the properties of local phenomena (e.g., dopants or defect sites in heterogeneous catalysts), the evolution of the band structure and the transition from semiconductor to metallic behavior in metal clusters, control of electronic structures of clusters through electron donating or withdrawing ligands, and the control of magnetic properties by interactions between the photoelectron and remnant neutral states, among other important topics of fundamental interest. This perspective revisits historical, groundbreaking anion PE spectroscopic finding and details more recent advances and insight gleaned from the PE spectra of small covalently or ionically bound clusters. The properties of the broad range of systems studied are uniquely small-cluster like in that incremental size differences are associated with striking changes in stability, electronic structures, and symmetry, but they can also be readily related to larger or bulk species in a broader range of materials and applications.

Deciphering the Phillips Catalyst by Orbital Analysis and Supervised Machine Learning from Cr Pre-edge XANES of Molecular Libraries.

Unveiling the nature and the distribution of surface sites in heterogeneous catalysts, and for the Phillips catalyst (CrO3/SiO2) in particular, is still a grand challenge despite more than 60 years of research. Commonly used references in Cr K-edge XANES spectral analysis rely on bulk materials (Cr-foil, Cr2O3) or molecules (CrCl3) that significantly differ from actual surface sites. In this work, we built a library of Cr K-edge XANES spectra for a series of tailored molecular Cr complexes, varying in oxidation state, local coordination environment, and ligand strength. Quantitative analysis of the pre-edge region revealed the origin of the pre-edge shape and intensity distribution. In particular, the characteristic pre-edge splitting observed for Cr(III) and Cr(IV) molecular complexes is directly related to the electronic exchange interactions in the frontier orbitals (spin-up and -down transitions). The series of experimental references was extended by theoretical spectra for potential active site structures and used for training the Extra Trees machine learning algorithm. The most informative features of the spectra (descriptors) were selected for the prediction of Cr oxidation states, mean interatomic distances in the first coordination sphere, and type of ligands. This set of descriptors was applied to uncover the site distribution in the Phillips catalyst at three different stages of the process. The freshly calcined catalyst consists of mainly Cr(VI) sites. The CO-exposed catalyst contains mainly Cr(II) silicates with a minor fraction of Cr(III) sites. The Phillips catalyst exposed to ethylene contains mainly highly coordinated Cr(III) silicates along with unreduced Cr(VI) sites.

Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

The atomic scale structure of the active sites in heterogeneous catalysts is central to their reactivity and selectivity. Therefore, understanding active site stability and evolution under different reaction conditions is key to the design of efficient and robust catalysts. Herein we describe theoretical calculations which predict that carbon monoxide can be used to stabilize different active site geometries in bimetallic alloys and then demonstrate experimentally that the same PdAu bimetallic catalyst can be transitioned between a single-atom alloy and a Pd cluster phase. Each state of the catalyst exhibits distinct selectivity for the dehydrogenation of ethanol reaction with the single-atom alloy phase exhibiting high selectivity to acetaldehyde and hydrogen versus a range of products from Pd clusters. First-principles based Monte Carlo calculations explain the origin of this active site ensemble size tuning effect, and this work serves as a demonstration of what should be a general phenomenon that enables in situ control over catalyst selectivity.

Mechanisms of the Catalytic Hydrochlorination of Acetylene: Active Sites, Isotope Effects, and Stereoselectivity

The mechanisms of acetylene vapour-phase hydrochlorination over chloro complexes of noble metals were reviewed. The nature of the active sites of heterogeneous catalysts, isotope effects of HCl/DCl, stereochemistry of reaction products, possible stepwise mechanisms, and mechanisms of individual steps were considered.

Perspective of Surfactant‐Free Colloidal Nanoparticles in Heterogeneous Catalysis

AbstractDue to material gaps and synthesis‐related cross‐correlations in heterogeneous catalysis, chemists and physicists are constantly motivated to develop novel catalyst preparation methods for independent control of morphology, size, and composition. Within this article, advances, opportunities, and the current limits of laser‐based catalyst preparation technique, as well as synergies with conventional methods will be reviewed in terms of purity, particle size, morphology, composition, and nanoparticle‐support interaction. It will be shown, that the surfactant‐free particles represent ideal model materials to validate kinetic models and conduct parametric activity studies by independent adjustment of functional properties like nanoparticle size, composition, and load. Consequently, the importance of transient plasma dynamics tailoring nanoparticle formation will be pointed out, comparing experimental studies with own calculations and novel simulations taken from literature. Finally, perspectives of surfactant‐free colloidal nanoparticles for unrevealing active sites in heterogeneous catalysts are presented.

Normalizing Hetereogeneous Electrocatalytic and Photocatalytic Rates.

This short essay urges the community of those who study electrocatalysis and photocatalysis to report measures of the number of active sites in heterogeneous catalysts (especially the redox sites in an electrocatalyst) and the number of photons involved in photoconversions. An example of the former is the use of CO stripping for catalysts containing platinum-group metals and N2O titration to count redox sites in supported electrocatalysts containing base metals that do not strongly chemisorb CO or hydrogen. A minimal example of the latter is to report energy density as a way to bridge between batch photolysis and flow photoinitiated reactions.