Reactant-Induced Structural Evolution of Pt Catalysts Confined in Zeolite.

Reactant-induced structural evolutions of heterogeneous metal catalysts are frequently observed in numerous catalytic systems, which can be associated with the formation or deactivation of active sites. In this work, we will show the structural transformation of subnanometer Pt clusters in pure-silica MFI zeolite structure in the presence of CO, O2, and/or H2O and the catalytic consequences of the Pt-zeolite materials derived from various treatment conditions. By applying the appropriate pretreatment under a reactant atmosphere, we can precisely modulate the size distribution of Pt species spanning from single Pt atoms to small Pt nanoparticles (1-5 nm) in the zeolite matrix, resulting in the desirably active and stable Pt species for CO oxidation. We also show the incorporation of Fe into the zeolite framework greatly promotes the stability of Pt species against undesired sintering under harsh conditions (up to 650 °C in the presence of CO, O2, and moisture).

Generation of Subnanometer Metal Clusters in Silicoaluminate Zeolites as Bifunctional Catalysts.

Zeolite-encapsulated subnanometer metal catalysts are an emerging class of solid catalysts with superior performances in comparison to metal catalysts supported on open-structure solid carriers. Currently, there is no general synthesis methodology for the encapsulation of subnanometer metal catalysts in different zeolite structures. In this work, we will show a general synthesis method for the encapsulation of subnanometer metal clusters (Pt, Pd, and Rh) within various silicoaluminate zeolites with different topologies (MFI, CHA, TON, MOR). The successful generation of subnanometer metal species in silicoaluminate zeolites relies on the introduction of Sn, which can suppress the migration of subnanometer metal species during high-temperature oxidation-reduction treatments according to advanced electron microscopy and spectroscopy characterizations. The advantage of encapsulated subnanometer Pt catalysts in silicoaluminate zeolites is reflected in the direct coupling of ethane and benzene for production of ethylbenzene, in which the Pt and the acid sites work in a synergistic way.

Photoexcitation of Fe3 O Nodes in MOF Drives Water Oxidation at pH=1 When Ru Catalyst Is Present.

Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco-friendly solar fuels. However, systems with light-driven water oxidation reaction (WOR) at pH=1 are rare. Broadly used [Ru(bpy)3 ]2+ (bpy=2,2'-bipyridine) photosensitizer has a fixed +1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe2 O3 , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe-based metal-organic framework (MOF) water oxidation photoelectrocatalysts active at pH=1 are presented. Fe-MIL-126 and Fe MOF-dcbpy structures were formed with 4,4'-biphenyl dicarboxylate (bpdc), 2,2'-bipyridine-5,5'-dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metal-based catalysts via coordination to 2,2'-bipyridine fragments. Fe-based MOFs were doped with Ru-based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H2 O)2 ]2+ WOC. Materials were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra-red (FTIR) spectroscopy, resonance Raman, X-ray absorption spectroscopy, fs optical pump-probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, FeIII and RuIII oxidation states are present, indicating rate-limiting electron transfer in MOF. Fe3 O nodes emerge as photosensitizers able to drive prolonged O2 evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru-WOC modification for faster WOC catalysis, or Ru-WOC substitution to 3d metal-based systems. The findings give further insight for development of light-driven water splitting systems based on Earth-abundant metals.

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications.

The Lewis/Brønsted catalytic properties of the Metal-Organic Framework (MOF) nodes can be tuned by simply controlling the solvent employed in the synthetic procedure. In this work, we demonstrate that Hf-MOF-808 can be prepared from a material with a higher amount of Brønsted acid sites, via modulated hydrothermal synthesis, to a material with a higher proportion of unsaturated Hf Lewis acid sites, via modulated solvothermal synthesis. The Lewis/Brønsted acid properties of the resultant metallic clusters have been studied by different characterization techniques, including XAS, FTIR and NMR spectroscopies, combined with a DFT study. The different nature of the Hf-MOF-808 materials allows their application as selective catalysts in different target reactions requiring Lewis, Brønsted or Lewis-Brønsted acid pairs.

MOF-Mediated Synthesis of Supported Fe-Doped Pd Nanoparticles under Mild Conditions for Magnetically Recoverable Catalysis*.

Metal-organic framework (MOF)-driven synthesis is considered as a promising alternative for the development of new catalytic materials with well-designed active sites. This synthetic approach is used here to gradually transform a new bimetallic MOF, with Pd and Fe as the metal components, by the in situ generation of aniline under mild conditions. This methodology results in a compositionally homogeneous nanocomposite formed by Fe-doped Pd nanoparticles that, in turn, are supported on iron oxide-doped carbon. The nanocomposite has been fully characterized by several techniques such as IR and Raman spectroscopy, TEM, XPS, and XAS. The performance of this nanocomposite as an heterogeneous catalyst for hydrogenation of nitroarenes and nitrobenzene coupling with benzaldehyde has been evaluated, proving it to be an efficient and reusable catalyst.

Regioselective Generation of Single-Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite.

Preparation of supported metal catalysts with uniform particle size and coordination environment is a challenging and important topic in materials chemistry and catalysis. In this work, we report the regioselective generation of single-site Ir atoms and their evolution into stabilized subnanometric Ir clusters in MWW zeolite, which are located at the 10MR window connecting the two neighboring 12MR supercages. The size of the subnanometric Ir clusters can be controlled by the post-synthesis treatments and maintain below 1 nm even after being reduced at 650 °C, which cannot be readily achieved with samples prepared by conventional impregnation methods. The high structure sensitivity, size-dependence, of catalytic performance in the alkane hydrogenolysis reaction of Ir clusters in the subnanometric regime is evidenced.

Determination of the Evolution of Heterogeneous Single Metal Atoms and Nanoclusters under Reaction Conditions: Which Are the Working Catalytic Sites?

Identification of active sites in heterogeneous metal catalysts is critical for understanding the reaction mechanism at the molecular level and for designing more efficient catalysts. Because of their structural flexibility, subnanometric metal catalysts, including single atoms and clusters with a few atoms, can exhibit dynamic structural evolution when interacting with substrate molecules, making it difficult to determine the catalytically active sites. In this work, Pt catalysts containing selected types of Pt entities (from single atoms to clusters and nanoparticles) have been prepared, and their evolution has been followed, while they were reacting in a variety of heterogeneous catalytic reactions, including selective hydrogenation reactions, CO oxidation, dehydrogenation of propane, and photocatalytic H2 evolution reaction. By in situ X-ray absorption spectroscopy, in situ IR spectroscopy, and high-resolution electron microscopy techniques, we will show that some characterization techniques carried out in an inadequate way can introduce confusion on the interpretation of coordination environment of highly dispersed Pt species. Finally, the combination of catalytic reactivity and in situ characterization techniques shows that, depending on the catalyst-reactant interaction and metal-support interaction, singly dispersed metal atoms can rapidly evolve into metal clusters or nanoparticles, being the working active sites for those abovementioned heterogeneous reactions.

A flexible cell for in situ combined XAS-DRIFTS-MS experiments.

A new cell for in situ combined X-ray absorption, diffuse reflectance IR Fourier transform and mass spectroscopies (XAS-DRIFTS-MS) is presented. The cell stands out among others for its achievements and flexibility. It is possible to perform XAS measurements in transmission or fluorescence modes, and the cell is compatible with external devices like UV-light and Raman probes. It includes different sample holders compatible with the different XAS detection modes, different sample forms (free powder or self-supporting pellet) and different sample loading/total absorption. Additionally, it has a small dead volume and can operate over a wide range of temperature (up to 600°C) and pressure (up to 5 bar). Three research examples will be shown to illustrate the versatility of the cell. This cell covers a wider range of applications than any other cell currently known for this type of study.

Generation of gold nanoclusters encapsulated in an MCM-22 zeolite for the aerobic oxidation of cyclohexane.

In this work, we will report the generation of Au clusters in a purely siliceous MCM-22 zeolite. The catalytic properties of these Au clusters have been tested for the selective oxidation of cyclohexane to cyclohexanol and cyclohexanone (KA-oil). The Au clusters encapsulated in the MCM-22 zeolite are highly active and selective for the oxidation of cyclohexane to KA-oil, which is superior to Au nanoparticles on the same support. These results suggest that Au clusters are highly active for the activation of oxygen to produce radical species.

Accuracy of Timed Up and Go Test for screening risk of falls among community-dwelling elderly / Acurácia do Timed Up and Go Test para rastrear risco de quedas em idosos da comunidade

OBJECTIVE: To determine the accuracy of the Timed Up and Go Test (TUGT) for screening the risk of falls among community-dwelling elderly individuals. METHOD: This is a prospective cohort study with a randomly by lots without reposition sample stratified by proportional partition in relation to gender involving 63 community-dwelling elderly individuals. Elderly individuals who reported having Parkinson's disease, a history of transitory ischemic attack, stroke and with a Mini Mental State Exam lower than the expected for the education level, were on a wheelchair and that reported a single fall in the previous six months were excluded. The TUGT, a mobility test, was the measure of interested and the occurrence of falls was the outcome. The performance of basic activities of daily living (ADL) and instrumental activities of daily living (IADL) was determined through the Older American Resources and Services, and the socio-demographic and clinical data were determined through the use of additional questionnaires. Receiver Operating Characteristic Curves were used to analyze the sensitivity and specificity of the TUGT. RESULTS: Elderly individuals who fell had greater difficulties in ADL and IADL (p<0.01) and a slower performance on the TUGT (p=0.02). No differences were found in socio-demographic and clinical characteristics between fallers and non-fallers. Considering the different sensitivity and specificity, the best predictive value for discriminating elderly individuals who fell was 12.47 seconds [(RR=3.2) 95%CI: 1.3-7.7]. CONCLUSIONS: The TUGT proved to be an accurate measure for screening the risk of falls among elderly individuals. Although different from that reported in the international literature, the 12.47 second cutoff point seems to be a better predictive value for Brazilian elderly individuals.

OBJETIVO: Determinar a acurácia do Timed Up and Go Test (TUGT) para rastrear risco de quedas em idosos da comunidade. MÉTODO: Trata-se de um estudo de coorte prospectivo com amostra sorteada aleatoriamente, sem reposição e estratificada por partilha proporcional em relação ao sexo de 63 idosos da comunidade. Excluíram-se idosos com doença de Parkinson, ataque isquêmico transitório, acidente vascular encefálico, Miniexame do Estado Mental inferior ao considerado normal de acordo com a escolaridade, movimentação exclusiva por cadeira de rodas e relato de uma queda nos seis meses anteriores à primeira entrevista. O TUGT, um teste de mobilidade, foi a medida testada, e o desfecho, a ocorrência de queda. Mensuraram-se atividades básicas (ABVD) e instrumentais de vida diária (AIVD) pela Older American Resources and Services e dados sociodemográficos e clínicos por questionário complementar. Para analisar a sensibilidade e a especificidade do TUGT, utilizou-se a Receiver Operating Characteristic Curves (ROC). RESULTADOS: Os idosos que caíram tinham maior dificuldade na execução de ABVD e AIVD (p<0,01) e desempenho mais lento no TUGT (p=0,02). Quanto às características sociodemográficas e clínicas, não houve diferença entre idosos que caíram e os que não caíram. Considerando as diferentes sensibilidades, especificidades e razões de verossimilhança, o melhor valor preditivo para discriminar idosos que caíram foi 12,47 segundos [(RR=3,2) IC95%: 1,3-7,7]. CONCLUSÃO: O TUGT é acurado para rastrear risco de quedas em idosos. O cut-off de 12,47 segundos, embora diferente da literatura internacional, parece ser um melhor valor preditivo para idosos brasileiros.

Accuracy of Timed Up and Go Test for screening risk of falls among community-dwelling elderly.

OBJECTIVE: To determine the accuracy of the Timed Up and Go Test (TUGT) for screening the risk of falls among community-dwelling elderly individuals. METHOD: This is a prospective cohort study with a randomly by lots without reposition sample stratified by proportional partition in relation to gender involving 63 community-dwelling elderly individuals. Elderly individuals who reported having Parkinson's disease, a history of transitory ischemic attack, stroke and with a Mini Mental State Exam lower than the expected for the education level, were on a wheelchair and that reported a single fall in the previous six months were excluded. The TUGT, a mobility test, was the measure of interested and the occurrence of falls was the outcome. The performance of basic activities of daily living (ADL) and instrumental activities of daily living (IADL) was determined through the Older American Resources and Services, and the socio-demographic and clinical data were determined through the use of additional questionnaires. Receiver Operating Characteristic Curves were used to analyze the sensitivity and specificity of the TUGT. RESULTS: Elderly individuals who fell had greater difficulties in ADL and IADL (p<0.01) and a slower performance on the TUGT (p=0.02). No differences were found in socio-demographic and clinical characteristics between fallers and non-fallers. Considering the different sensitivity and specificity, the best predictive value for discriminating elderly individuals who fell was 12.47 seconds [(RR=3.2) 95%CI: 1.3-7.7]. CONCLUSIONS: The TUGT proved to be an accurate measure for screening the risk of falls among elderly individuals. Although different from that reported in the international literature, the 12.47 second cutoff point seems to be a better predictive value for Brazilian elderly individuals.