Two-dimensional band structure in honeycomb metal-organic frameworks

Metal-organic frameworks (MOFs) are an important class of materials that present intriguing opportunities in the fields of sensing, gas storage, catalysis, and optoelectronics. Very recently, two-dimensional (2D) MOFs have been proposed as a flexible material platform for realizing exotic quantum phases including topological and anomalous quantum Hall insulators. Experimentally, direct synthesis of 2D MOFs has been essentially confined to metal substrates, where the interaction with the substrate masks the intrinsic electronic properties of the MOF. Here, we demonstrate synthesis of 2D honeycomb metal-organic frameworks on a weakly interacting epitaxial graphene substrate. Using low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM) complemented by density-functional theory (DFT) calculations, we show the formation of 2D band structure in the MOF decoupled from the substrate. These results open the experimental path towards MOF-based designer quantum materials with complex, engineered electronic structures

Understanding the atomic-scale contrast in Kelvin Probe Force Microscopy

A numerical analysis of the origin of the atomic-scale contrast in Kelvin probe force microscopy (KPFM) is presented. Atomistic simulations of the tip-sample interaction force field have been combined with a non-contact Atomic Force Microscope/KPFM simulator. The implementation mimics recent experimental results on the (001) surface of a bulk alkali halide crystal for which simultaneous atomic-scale topographical and Contact Potential Difference (CPD) contrasts were reported. The local CPD does reflect the periodicity of the ionic crystal, but not the magnitude of its Madelung surface potential. The imaging mechanism relies on the induced polarization of the ions at the tip-surface interface owing to the modulation of the applied bias voltage. Our findings are in excellent agreement with previous theoretical expectations and experimental observations

DCU at the TREC 2008 Blog Track

In this paper we describe our system, experiments and re- sults from our participation in the Blog Track at TREC 2008. Dublin City University participated in the adhoc re- trieval, opinion finding and polarised opinion finding tasks. For opinion finding, we used a fusion of approaches based on lexicon features, surface features and syntactic features. Our experiments evaluated the relative usefulness of each of the feature sets and achieved a significant improvement on the baseline

Accelerated Thermal Aging of Fe-Zeolite SCR Catalysts on an Engine Bench

Selective catalytic reduction (SCR) of NOx with urea/NH3 is a leading candidate to the impending more stringent emissions regulations for diesel engines. Currently, there is no consensus on the durability and the deactivation mechanisms associated with zeolite-based SCR catalysts, nor is there an established protocol for rapidly aging zeolite-based SCR catalysts that replicates the catalyst deactivation associated with field service. A 517 cc single-cylinder, naturally-aspirated direct injection (NA/DI) diesel engine is used to perform accelerated thermal aging on Fe-zeolite SCR catalysts. The engine is fitted with an exhaust aftertreatment system consisting of a DOC, a SCR catalyst and a DPF. Accelerated aging protocol established for the SCR catalyst utilizes high temperature exhaust gases during the active regeneration of the DPF. Accelerated aging is carried out at exhaust gas temperatures of 650, 750 and 850°C at the SCR inlet and at a gas hourly space velocity (GHSV) of approximately 40,000 h-1. The engine is maintained at 1500 rpm and supplemental fuel is injected upstream of the DOC to alter the temperature of the aftertreatment system. The aged Fe-zeolite SCR catalysts are evaluated for NOx performance in a bench-flow reactor and characterized by multiple surface characterization techniques for materials changes. The NOx performance of the front sections of the engine-aged catalysts is severely degraded. BET surface area measurements of the engine-aged catalyst indicate a severe reduction of catalyst surface area in the front sections of the catalysts aged at 750 and 850°C. However, the catalyst aged at 650°C has a catalyst surface area similar to that of a fresh catalyst; thereby ruling out reduction of catalyst surface area as the sole cause of the catalyst deactivation seen in the front sections of the engine-aged catalysts. The similar shape of the NOx conversion profiles observed with these catalyst sections even at different aging temperatures indicates some type of catalyst poisoning; however, the cause of catalyst degradation in these catalyst sections is not identified in this investigation. There is a good relationship between the NOx performance and catalyst aging temperature for the rear sections of the engine-aged catalysts – NOx performance decreases with increasing aging temperature. XRD patterns and NO oxidation experiments reveal evidence of zeolite dealumination in the engine-aged catalysts. BET surface area measurements show that catalyst surface area decreases with increasing aging temperature, which further supports the suggestion of zeolite dealumination as the cause of catalyst deactivation in the rear sections of the engine-aged catalysts. A comparison between the engine-aged and field-aged catalysts is conducted to assess the validity of the implemented accelerated thermal aging protocol in replicating the aging conditions observed in the field-aged catalyst. Bench-flow reactor evaluation is used to determine the NOx performance of the engine-aged and field-aged catalysts, and in depth surface studies are used to determine the deactivation mechanisms associated with each type of catalyst aging. SEM micrographs and BET surface area measurements of the aged catalysts show that the deactivation mechanism associated with catalyst aging is primarily physical damage to the zeolite washcoat for both the field-aged and engine-aged catalysts. Furthermore, X-ray diffraction and NO oxidation experiments identify zeolite dealumination as the underlying cause of the washcoat degradation. Finally, BFR evaluation shows that the NOx performance of the catalyst aged at 750°C for approximately 50 hours compares very well to that of the field-aged catalyst with a service life of 3 years. It is concluded that accelerated thermal aging on the engine bench is successful in bringing about similar catalyst changes to those seen with the field-aged catalyst

Sampling and Inference for Beta Neutral-to-the-Left Models of Sparse Networks

Empirical evidence suggests that heavy-tailed degree distributions occurring in many real networks are well-approximated by power laws with exponents $\eta$ that may take values either less than and greater than two. Models based on various forms of exchangeability are able to capture power laws with $\eta < 2$, and admit tractable inference algorithms; we draw on previous results to show that $\eta > 2$ cannot be generated by the forms of exchangeability used in existing random graph models. Preferential attachment models generate power law exponents greater than two, but have been of limited use as statistical models due to the inherent difficulty of performing inference in non-exchangeable models. Motivated by this gap, we design and implement inference algorithms for a recently proposed class of models that generates $\eta$ of all possible values. We show that although they are not exchangeable, these models have probabilistic structure amenable to inference. Our methods make a large class of previously intractable models useful for statistical inference.Comment: Accepted for publication in the proceedings of Conference on Uncertainty in Artificial Intelligence (UAI) 201

Oncologic outcomes following surgical management of clinical stage II sex cord stromal tumors

Objective To investigate the clinical history of patients with clinical stage II sex cord stromal tumors who underwent RPLND at our institution. Methods Our prospectively maintained testicular cancer database was queried to identify patients who presented with or developed clinical stage II sex cord stromal tumors and underwent RPLND at our institution between 1980 and 2018. Demographic, clinical and pathological characteristics were reviewed. Kaplan-Meier curves were graphed to assess recurrence-free and overall survival. Results Fourteen patients were included in the study with a median age of 44.2 years. Four patients presented with clinical stage II disease and 10 patients developed metastatic disease during follow-up of initial clinical stage I disease with a median time to metastasis of 2.7 years (range: 0.4-19.5 years). Of the 10 patients with orchiectomy pathology data available, all patients had at least 1 risk factor on testis pathology (mean: 2.9 risk factors). Nine patients received treatment prior to referral to our institution. All patients recurred post-RPLND at Indiana University. Median recurrence-free survival was 9.8 months. Twelve patients died of disease with a median overall survival of 14.4 months. Conclusions Metastatic sex cord stromal tumors are rare and are more resistant to standard treatment modalities than metastatic germ cell tumors. Patients presenting with sex cord stromal tumors should consider prophylactic primary RPLND in the setting of one or more pathological predictor of malignancy