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    The SS-SCR Scheme for dynamic spectrum access

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    We integrate the two models of Cognitive Radio (CR), namely, the conventional Sense-and-Scavenge (SS) Model and Symbiotic Cooperative Relaying (SCR). The resultant scheme, called SS-SCR, improves the efficiency of spectrum usage and reliability of the transmission links. SS-SCR is enabled by a suitable cross-layer optimization problem in a multihop multichannel CR network. Its performance is compared for different PU activity patterns with those schemes which consider SS and SCR separately and perform disjoint resource allocation. Simulation results depict the effectiveness of the proposed SS-SCR scheme. We also indicate the usefulness of cloud computing for a practical deployment of the scheme

    5G ์ดํ›„ ๋ฌด์„  ๋„คํŠธ์›Œํฌ๋ฅผ ์œ„ํ•œ ๋ฌด์„  ์ ‘์† ๊ธฐ์ˆ  ํ–ฅ์ƒ ์—ฐ๊ตฌ

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    ํ•™์œ„๋…ผ๋ฌธ (๋ฐ•์‚ฌ) -- ์„œ์šธ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› : ๊ณต๊ณผ๋Œ€ํ•™ ์ „๊ธฐยท์ •๋ณด๊ณตํ•™๋ถ€, 2020. 8. ๋ฐ•์„ธ์›….Recently, operators are creating services using 5G systems in various fields, e.g., manufacturing, automotive, health care, etc. 5G use cases include transmission of small packets using IoT devices to high data rate transmission such as high-definition video streaming. When a large-scale IoT device transmits a small packet, power saving is important, so it is necessary to disconnect from the base station and then establish a connection through random access to transmit data. However, existing random access procedures are difficult to satisfy various latency requirements. It is attractive to use a wide bandwidth of the millimeter wave spectrum for high data rate transmission. In order to overcome the channel characteristics, beamforming technology is applied. However, when determining a beam pair between a transmitter and a receiver, interference is not considered. In this dissertation, we consider the following three enhancements to enable 5G and beyond use cases: (i) Two-step random access procedure for delay-sensitive devices, (ii) self-uplink synchronization framework for solving preamble collision problem, and (iii) interference-aware beam adjustment for interference coordination. First, RAPID, two-step random access for delay-sensitive devices, is proposed to reduce latency requirement value for satisfying specific reliability. When devices, performing RAPID and contention-based random access, coexist, it is important to determine a value that is the number of preambles for RAPID to reduce random access load. Simulation results show that RAPID achieves 99.999% reliability with 80.8% shorter uplink latency, and also decreases random access load by 30.5% compared with state-of-the-art techniques. Second, in order to solve preamble collision problem, we develop self-uplink synchronization framework called EsTA. Preamble collision occurs when multiple devices transmit the same preamble. Specifically, we propose a framework that helps the UE to estimate the timing advance command using a deep neural network model and to determine the TA value. Estimation accuracy can achieve 98โ€“99% when subcarrier spacing is 30 and 60 kHz. Finally, we propose IBA, which is interference-aware beam adjustment method to reduce interference in millimeter wave networks. Unlike existing methods of reducing interference by scheduling time and frequency resources differently, interference is controlled through beam adjustment. In IBA, it is important to reduce search space of finding new beam pair to reduce interference. In practical, it is impossible to search beam pair of all combinations. Therefore, through Monte Carlo method, we can reduce search space to achieve local optimum. IBA achieve enhancement of lower 50%throughput up to 50% compared with only applying beam adjustment. In summary, we propose a two-step random access, a self-uplink synchronization framework, and interference-aware beam adjustment for 5G and beyond use cases. Through these researches, we achieve enhancements of network performance such as latency and throughput compared with state-of-the-art techniques.์ตœ๊ทผ ์‚ฌ์—…์ž๋Š” ์ œ์กฐ, ์ž๋™์ฐจ, ํ—ฌ์Šค ์ผ€์–ด ๋“ฑ ๋‹ค์–‘ํ•œ ๋ถ„์•ผ์—์„œ 5G ์‹œ์Šคํ…œ์„ ์‚ฌ์šฉํ•˜์—ฌ ์„œ๋น„์Šค๋ฅผ ๋งŒ๋“ค๊ณ  ์žˆ๋‹ค. 5G ์‚ฌ์šฉ ์‚ฌ๋ก€์—๋Š” IoT ์žฅ์น˜๋ฅผ ์ด์šฉํ•œ ์ž‘์€ ํŒจํ‚ท ์ „์†ก์—์„œ๊ณ ํ™”์งˆ ๋น„๋””์˜ค ์ŠคํŠธ๋ฆฌ๋ฐ๊ณผ ๊ฐ™์€ ๊ณ ์† ๋ฐ์ดํ„ฐ ์ „์†ก๊นŒ์ง€ ํฌํ•จ๋œ๋‹ค. ๋Œ€๊ทœ๋ชจ IoT ์žฅ์น˜๊ฐ€์ž‘์€ ํŒจํ‚ท์„ ์ „์†กํ•˜๋Š” ๊ฒฝ์šฐ ์ „๋ ฅ ์†Œ๋ชจ ์ ˆ์•ฝ์ด ์ค‘์š”ํ•˜๋ฏ€๋กœ ๊ธฐ์ง€๊ตญ๊ณผ์˜ ์—ฐ๊ฒฐ์„ ๋Š์€๋‹ค์Œ ๋žœ๋ค ์•ก์„ธ์Šค๋ฅผ ํ†ตํ•ด ๋‹ค์‹œ ๊ธฐ์ง€๊ตญ๊ณผ ์—ฐ๊ฒฐํ•˜์—ฌ ๋ฐ์ดํ„ฐ๋ฅผ ์ „์†กํ•ด์•ผํ•œ๋‹ค. ๊ทธ๋Ÿฌ๋‚˜๊ธฐ์กด์˜ ๋žœ๋ค ์•ก์„ธ์Šค ์ ˆ์ฐจ๋Š” ๋‹ค์–‘ํ•œ ์ง€์—ฐ์‹œ๊ฐ„ ์š”๊ฑด์„ ๋งŒ์กฑ์‹œํ‚ค๊ธฐ ์–ด๋ ต๋‹ค. ํ•œํŽธ, ๋†’์€๋ฐ์ดํ„ฐ ์ „์†ก ์†๋„๋ฅผ ์œ„ํ•ด ๋„“์€ ๋Œ€์—ญํญ์˜ ๋ฐ€๋ฆฌ๋ฏธํ„ฐํŒŒ ๋Œ€์—ญ์„ ์‚ฌ์šฉํ•œ๋‹ค. ์ด๋•Œ, ๋ฐ€๋ฆฌ๋ฏธํ„ฐํŒŒ ๋Œ€์—ญ ์ฑ„๋„ ํŠน์„ฑ์„ ๊ทน๋ณตํ•˜๊ธฐ ์œ„ํ•ด ๋น”ํฌ๋ฐ ๊ธฐ์ˆ ์ด ์ ์šฉ๋œ๋‹ค. ๊ทธ๋Ÿฌ๋‚˜ ํ˜„์žฌ 5Gํ‘œ์ค€์—์„œ ์†ก์‹ ๊ธฐ์™€ ์ˆ˜์‹ ๊ธฐ ์‚ฌ์ด์˜ ๋น” ์Œ์„ ๊ฒฐ์ •ํ•  ๋•Œ, ๊ฐ„์„ญ์€ ๊ณ ๋ ค๋˜์ง€ ์•Š๋Š”๋‹ค. ์ด๋…ผ๋ฌธ์—์„œ๋Š” 5G ๋ฐ ๊ทธ ์ดํ›„์˜ ๋„คํŠธ์›Œํฌ์—์„œ ๋‹ค์–‘ํ•œ ์‚ฌ์šฉ ์‚ฌ๋ก€๋ฅผ ์ง€์›ํ•˜๊ธฐ ์œ„ํ•ด ๋‹ค์Œ์„ธ ๊ฐ€์ง€ ๊ฐœ์„  ์‚ฌํ•ญ์„ ๊ณ ๋ คํ•œ๋‹ค. (i) ์ง€์—ฐ์— ๋ฏผ๊ฐํ•œ ์žฅ์น˜๋ฅผ ์œ„ํ•œ 2 ๋‹จ๊ณ„ ๋žœ๋ค ์•ก์„ธ์Šค์ ˆ์ฐจ, (ii) ํ”„๋ฆฌ์•ฐ๋ธ” ์ถฉ๋Œ ๋ฌธ์ œ๋ฅผ ํ•ด๊ฒฐํ•˜๊ธฐ ์œ„ํ•œ ์ž์ฒด ์ƒํ–ฅ๋งํฌ ๋™๊ธฐํ™” ํ”„๋ ˆ์ž„ ์›Œํฌ,๊ทธ๋ฆฌ๊ณ  (iii) ๊ฐ„์„ญ์„ ์ค„์ด๊ธฐ ์œ„ํ•œ ๊ฐ„์„ญ ์ธ์‹ ๋น” ์กฐ์ •์ด๋‹ค. ์ฒซ์งธ, ์ง€์—ฐ์— ๋ฏผ๊ฐํ•œ ์žฅ์น˜๋ฅผ ์œ„ํ•œ 2 ๋‹จ๊ณ„ ๋žœ๋ค ์•ก์„ธ์Šค์ธ RAPID๋Š” ํŠน์ • ์‹ ๋ขฐ๋„๋ฅผ ๋งŒ์กฑ์‹œํ‚ค๊ธฐ ์œ„ํ•œ ์ง€์—ฐ์‹œ๊ฐ„์„ ์ค„์ด๊ธฐ ์œ„ํ•ด ์ œ์•ˆ๋˜์—ˆ๋‹ค. RAPID์™€ ๊ฒฝํ•ฉ ๊ธฐ๋ฐ˜ ๋žœ๋ค ์•ก์„ธ์Šค๋ฅผ ์ˆ˜ํ–‰ํ•˜๋Š” ์žฅ์น˜๊ฐ€ ๊ณต์กดํ•  ๊ฒฝ์šฐ RAPID๊ฐ€ ๋žœ๋ค ์•ก์„ธ์Šค ๋ถ€ํ•˜๋ฅผ ์ค„์ด๊ธฐ ์œ„ํ•ด RAPID๋ฅผ ์œ„ํ•ด ํ• ๋‹น๋˜๋Š” ํ”„๋ฆฌ์•ฐ๋ธ” ์ˆ˜๋ฅผ ๊ฒฐ์ •ํ•˜๋Š” ๊ฒƒ์ด ์ค‘์š”ํ•˜๋‹ค. ์‹œ๋ฎฌ๋ ˆ์ด์…˜ ๊ฒฐ๊ณผ์— ๋”ฐ๋ฅด๋ฉด RAPID๋Š” 99.999%์˜์‹ ๋ขฐ๋„๋ฅผ ๋งŒ์กฑ์‹œํ‚ค๋Š” ์ง€์—ฐ์‹œ๊ฐ„์„ ์ตœ์‹  ๊ธฐ์ˆ ์— ๋น„ํ•ด 80.8% ์ค„์ด๋ฉด์„œ, ๋žœ๋ค ์•ก์„ธ์Šค๋ถ€ํ•˜๋ฅผ 30.5% ์ค„์ธ๋‹ค. ๋‘˜์งธ, ํ”„๋ฆฌ์•ฐ๋ธ” ์ถฉ๋Œ ๋ฌธ์ œ๋ฅผ ํ•ด๊ฒฐํ•˜๊ธฐ ์œ„ํ•ด ์ž์ฒด ์ƒํ–ฅ๋งํฌ ๋™๊ธฐํ™” ํ”„๋ ˆ์ž„์›Œํฌ์ธ EsTA๋ฅผ ๊ฐœ๋ฐœํ•œ๋‹ค. ํ”„๋ฆฌ์•ฐ๋ธ” ์ถฉ๋Œ์€ ์—ฌ๋Ÿฌ ์žฅ์น˜๊ฐ€ ๋™์ผํ•œ ํ”„๋ฆฌ์•ฐ๋ธ”์„ ์ „์†กํ•  ๋•Œ ๋ฐœ์ƒํ•œ๋‹ค. ๊ตฌ์ฒด์ ์œผ๋กœ, ๋‹จ๋ง์ด ์‹ฌ์ธต ์‹ ๊ฒฝ๋ง ๋ชจ๋ธ์„ ์‚ฌ์šฉํ•˜์—ฌ timing advance(TA) command๋ฅผ ์ถ”์ •ํ•˜๊ณ  TA๊ฐ’์„ ๊ฒฐ์ •ํ•˜๋Š” ํ”„๋ ˆ์ž„ ์›Œํฌ๋ฅผ ์ œ์•ˆํ•œ๋‹ค. ๋„คํŠธ์›Œํฌ ์‹œ์Šคํ…œ์˜ ๋ถ€๋ฐ˜์†กํŒŒ ๊ฐ„๊ฒฉ์ด 30 ๋ฐ 60 kHz ์ผ ๋•Œ, TA command ์ถ”์ • ์ •ํ™•๋„๋Š”98โ€“99%๋ฅผ ๋‹ฌ์„ฑ ํ•  ์ˆ˜ ์žˆ๋‹ค. ๋งˆ์ง€๋ง‰์œผ๋กœ, ๋ฐ€๋ฆฌ๋ฏธํ„ฐํŒŒ ๋„คํŠธ์›Œํฌ์—์„œ ๊ฐ„์„ญ์„ ์ค„์ด๊ธฐ ์œ„ํ•œ ๊ฐ„์„ญ ์ธ์‹ ๋น” ์กฐ์ • ๋ฐฉ๋ฒ•์ธ IBA๋ฅผ ์ œ์•ˆํ•œ๋‹ค. ์‹œ๊ฐ„๊ณผ ์ฃผํŒŒ์ˆ˜ ์ž์›์„ ๋‹ค๋ฅด๊ฒŒ ์˜ˆ์•ฝํ•˜์—ฌ ๊ฐ„์„ญ์„ ์ค„์ด๋Š” ๊ธฐ์กด์˜ ๋ฐฉ๋ฒ•๊ณผ ๋‹ฌ๋ฆฌ IBA๋Š” ๋น” ์กฐ์ •์„ ํ†ตํ•ด ๊ฐ„์„ญ์„ ์ œ์–ดํ•œ๋‹ค.์ด ๋•Œ, ๊ฐ„์„ญ์„ ์ค„์ด๊ธฐ ์œ„ํ•ด ์ƒˆ๋กœ์šด ๋น” ์Œ์„ ์ฐพ๋Š” ๊ฒ€์ƒ‰ ๊ณต๊ฐ„์„ ์ค„์ด๋Š” ๊ฒƒ์ด ์ค‘์š”ํ•˜๋‹ค.ํ˜„์‹ค์ ์œผ๋กœ ๋ชจ๋“  ๋น” ์Œ์˜ ์กฐํ•ฉ์„ ๊ฒ€์ƒ‰ํ•˜๋Š” ๊ฒƒ์€ ๋ถˆ๊ฐ€๋Šฅํ•˜๋‹ค. ๋”ฐ๋ผ์„œ IBA๋Š” Monte Carlo ๋ฐฉ๋ฒ•์„ ํ†ตํ•ด ๊ฒ€์ƒ‰ ๊ณต๊ฐ„์„ ์ถ•์†Œํ•˜์—ฌ local optimum์„ ๋‹ฌ์„ฑํ•˜๋„๋ก ์„ค๊ณ„๋˜์–ด์•ผํ•œ๋‹ค. IBA๋Š” 5G ํ‘œ์ค€์˜ ๋น” ์กฐ์ • ๋ฐฉ๋ฒ•๊ณผ ๋น„๊ตํ–ˆ์„ ๋•Œ, ํ•˜์œ„ 50% throughput์˜ ์ค‘๊ฐ„๊ฐ’์ด์ตœ๋Œ€ 50%๊นŒ์ง€ ํ–ฅ์ƒ๋œ๋‹ค. ์š”์•ฝํ•˜๋ฉด, ์šฐ๋ฆฌ๋Š” 5G ๋ฐ ๊ทธ ์ดํ›„์˜ ๋‹ค์–‘ํ•œ ์‚ฌ์šฉ ์‚ฌ๋ก€๋ฅผ ์œ„ํ•ด์„œ 2 ๋‹จ๊ณ„ ๋žœ๋ค ์•ก์„ธ์Šค, ์ž์ฒด ์ƒํ–ฅ๋งํฌ ๋™๊ธฐํ™” ํ”„๋ ˆ์ž„ ์›Œํฌ, ๊ทธ๋ฆฌ๊ณ  ๊ฐ„์„ญ ์ธ์‹ ๋น”์กฐ์ • ๋ฐฉ๋ฒ•์„ ์ œ์•ˆํ•œ๋‹ค. ์ด ์—ฐ๊ตฌ๋ฅผ ํ†ตํ•ด ์ตœ์‹  ๊ธฐ์ˆ ์— ๋น„ํ•ด ์ง€์—ฐ์‹œ๊ฐ„ ๋ฐ ์ฒ˜๋ฆฌ๋Ÿ‰๊ณผ ๊ฐ™์€๋„คํŠธ์›Œํฌ ์„ฑ๋Šฅ์ด ํ–ฅ์ƒ๋œ๋‹ค.1 Introduction 1 1.1 5G Vision, Applications, and Keywords 1 1.2 Overview of Existing Approach 3 1.3 Main Contributions 4 1.3.1 RAPID: Two-Step Random Access 4 1.3.2 EsTA: Self-Uplink Synchronization 5 1.3.3 IBA: Interference-Aware Beam Adjustment 5 1.4 Organization of the Dissertation 6 2 RAPID: Contention Resolution-based Random Access Procedure using Context ID for IoT 7 2.1 Introduction 7 2.2 Background 10 2.2.1 RRC State 10 2.2.2 Random Access Procedure 11 2.2.3 Uplink Latency in RRC INACTIVE State 13 2.2.4 Related Work 14 2.3 RAPID: Proposed Random Access Procedure 15 2.3.1 Overview 15 2.3.2 Criterion of Applying RAPID 16 2.3.3 Preamble Set and RACH Period Allocation 17 2.3.4 Preamble Transmission 18 2.3.5 RAR Transmission 19 2.3.6 AS Context ID Allocation 21 2.3.7 Number of Preambles for RAPID 22 2.4 Access Pattern Analyzer 22 2.4.1 Overview 22 2.4.2 APA Operation 23 2.4.3 Margin Value 26 2.4.4 Offset Index Decision 26 2.5 Random Access Load Analysis 27 2.5.1 System Model 28 2.5.2 Markov Chain Model for 4-Step RA 29 2.5.3 Average Random Access Load for 4-Step RA 34 2.5.4 Markov Chain Model for RAPID 34 2.5.5 Average Random Access Load for RAPID 37 2.5.6 Validation of Analysis 38 2.5.7 Optimization Problem 41 2.6 Performance Evaluation 42 2.6.1 Simulation Setup 42 2.6.2 Number of Preambles for RAPID 43 2.6.3 Performance of RAPID 43 2.6.4 Performance of APA 48 2.7 Summary 48 3 EsTA: Self-Uplink Synchronization in 2-Step Random Access 49 3.1 Introduction 49 3.2 Background 51 3.2.1 Overview of 2-Step CBRA 51 3.2.2 Channel Structure for msgA 52 3.2.3 TA Handling for the Payload 54 3.2.4 2-Step Random Access in Recent Literature 56 3.3 Challenges of 2-Step Random Access 57 3.3.1 Preamble Allocation 57 3.3.2 Resource Mapping for msgA 58 3.3.3 DFT Operation in gNB 58 3.3.4 Detected Collision Problem 58 3.4 EsTA: Proposed Self-UL Synchronization Procedure 59 3.4.1 Overview 60 3.4.2 Overall Procedures 60 3.4.3 Performance Evaluation 61 3.4.4 Future Research Perspectives 65 3.5 Summary 65 4 IBA: Interference-Aware Beam Adjustment for 5G mmWave Networks 67 4.1 Introduction 67 4.2 Background 68 4.2.1 Beam Management in 5G NR 68 4.2.2 System-Level Simulation and 3D Beamforming for 5G NR 70 4.3 Motivation 70 4.3.1 Throughput Degradation by Interference 70 4.4 IBA: Proposed Interference Management Scheme 72 4.4.1 Overall Procedure 72 4.4.2 Reduction of Search Space 72 4.4.3 Algorithm for IBA 75 4.5 Performance Evaluation 76 4.6 Summary 78 5 Concluding Remarks 79 5.1 Research Contributions 79 5.2 Future Work 80 Abstract (In Korean) 89 ๊ฐ์‚ฌ์˜ ๊ธ€ 92Docto

    Fundamental studies on copper zeolites for catalytic NO x abatement

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    Stringent regulations in mobile NOx emissions have resulted in the development of Standard Selective Catalytic Reduction (SCR) as the dominant NOx abatement technology in lean burn diesel engines. Standard SCR is a reaction of nitric oxide (NO) with ammonia (NH3), in the presence of oxygen (O 2) to form nitrogen (N2) and water (H2O). Copper containing zeolites show commercially viable SCR performance. Cu-SSZ-13 (CHA framework), a member of this family, is a preferred catalyst for SCR applications because it shows exceptional hydrothermal stability in addition to commercially viable SCR performance. Our work focuses on 1) determination of the active sites, and 2) elucidation of the dominant reaction steps on active sites, for standard SCR (at 473 K) and catalytic oxidation of NO (at 550 K), over Cu-SSZ-13.^ A series of Cu-SSZ-13 catalysts (Si:Al = 4.5) tested for standard SCR kinetics exhibited a linear increase in the rate of nitrogen production (per gram catalyst) with Cu:Al ratio till Cu:Al = 0.2. Separate catalyst characterization tools like Ultra-Violet-Visible-Near Infra-red (UV-Vis-NIR) spectroscopy under ambient conditions, X-ray Absorption Near Edge structure (XANES) of Cu ions during standard SCR, Density Functional Theory (DFT) calculations, and titration of residual acid sites with amine titrants on this series of catalysts established isolated Cu ions ion exchanged at the framework Al sites in six member rings of SSZ-13 as the dominant Cu ion configuration below Cu:Al = 0.2, which we assign as the dominant active sites for low temperature standard SCR (T = 473 K). Above Cu:Al = 0.2, Cu ion clusters (CuxOy) were formed, which stabilized on framework Al sites at favorable distances, in the eight member cage of SSZ-13. CuxOy was active in catalyzing dry NO oxidation to NO2 via oxygen activation mediated by local Cu-Oy-Cu bonds. The density of local Cu-Oy-Cu bonds was quantified from in-situ XANES under NO oxidation and correlated linearly with the rate of NO oxidation, thereby establishing CuxOy as the active sites for NO oxidation. NO oxidation was also explored on catalysts prepared to contain exclusively isolated Cu(II) ions and the Gibbs free energy of reaction intermediates was shown to be higher than the free energy of similar intermediates formed from local Cu-O y-Cu bonds, consistent with the experimental observation of experimentally undetectable rate of NO oxidation on isolated Cu(II) ions in the six member rings of SSZ-13. As a result, dry NO oxidation is proposed as a probe reaction to detect Cu ion clustering in Cu-SSZ-13 formulations.^ Operando XANES during standard SCR also implicated isolated Cu ions (in the six member SSZ-13 ring) as the active site; however, the +2 oxidation state of Cu is not preserved. Experimental XANES analysis during appropriate reactant cutoff from steady state standard SCR and DFT calculated Gibbs free energy analysis of adsorbates under reaction conditions point toward a Cu ion redox between Cu(I) and Cu(II) to mediate standard SCR. The isolated Cu(II) ion reduction is achieved by both NO and NH3 to make nitrogen, isolated Cu(I) ions, and experimentally detectable proximal Brรธnsted acidic sites. These proximal acid sites can stabilize ammonium ions during standard SCR catalysis, while NO and O2 oxidize the Cu(I) back to Cu(II) via nitrite (NO2-) intermediate formation, as predicted by DFT. The close proximity between nitrites (on Cu) and ammonium ions (on proximal Brรธnsted acid sites) enable the formation of nitrogen and water via an intermediate which resembles ammonium nitrite, thereby completing the catalytic cycle. These findings highlight the bi-functional nature of Cu-SSZ-13 displayed by a close proximity of Bronsted acidic sites and redox metal ion centers which work in concert to catalyze the selective reduction of NO with NH3 in the presence of oxygen, to form nitrogen and water

    Electron-hole spectra created by adsorption on metals from density-functional theory

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    Non-adiabaticity in adsorption on metal surfaces gives rise to a number of measurable effects, such as chemicurrents and exo-electron emission. Here we present a quantitative theory of chemicurrents on the basis of ground-state density-functional theory (DFT) calculations of the effective electronic potential and the Kohn-Sham band structure. Excitation probabilities are calculated both for electron-hole pairs and for electrons and holes separately from first-order time-dependent perturbation theory. This is accomplished by evaluating the matrix elements (between Kohn-Sham states) of the rate of change of the effective electronic potential between subsequent (static) DFT calculations. Our approach is related to the theory of electronic friction, but allows for direct access to the excitation spectra. The method is applied to adsorption of atomic hydrogen isotopes on the Al(111) surface. The results are compatible with the available experimental data (for noble metal surfaces); in particular, the observed isotope effect in H versus D adsorption is described by the present theory. Moreover, the results are in qualitative agreement with computationally elaborate calculations of the full dynamics within time-dependent density-functional theory, with the notable exception of effects due to the spin dynamics. Being a perturbational approach, the method proposed here is simple enough to be applied to a wide class of adsorbates and surfaces, while at the same time allowing us to extract system-specific information.Comment: 23 pages, 9 figures, accepted for publication in Phys. Rev. B, http://prb.aps.org/, v2: some major improvements, plus correction of minor error

    Analysis of the physical properties and photoelectrochemical behavior of c-Si/a-SiC:H(p) photocathodes for solar water splitting

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    Photoelectrochemical (PEC) processes have become an efficient and viable method for solar energy conversion into zero-emission fuels by harnessing and storage the power of the sun, which offers an environment-friendly approach. Hydrogen is considered as a sustainable and suitable energy alternative in comparison to energy systems based on the consumption of conventional hydrocarbon fuels. In particular, hydrogen production by PEC water splitting represents an attractive alternative to enhance the efficiency of water splitting process using sun light. Current research in this field is devoted to the fabrication and evaluation of new photoactive materials that upon sunlight absorption enable water-splitting PEC reactions with high efficiency and durability. Silicon based compounds offer a good opportunity as photoactive material due to its high abundance and current scalable technologies. Silicon is the eighth most abundant element in the universe and constitutes up to 27.2% of the earthโ€™s crust weight [1]. Particularly, hydrogenated amorphous silicon carbide (a-SiC:H) thin films have been tested as photocathode material for photo-assisted electrolysis, exhibiting solar to hydrogen conversion efficiencies up to 7.5 %. Due to the capability to tailor the bandgap (1.8 - 3.3 eV) by the incorporation of carbon in a-Si:H, this material has turned out to be a promising candidate for PEC cells, fulfilling the optical bandgap (Egap) primary requirement, i.e. Egap > 2.2 eV. Additionally, the carbon incorporation leads to an enhancement of the corrosion resistance properties in aqueous media. It has been theoretically estimated that a PEC device with an a-Si0.9C0.1:H absorption layer exhibiting 2.0 eV of energy bandgap, can generate a photocurrent density Jph of 15 mA/cm2 (solar-to-hydrogen conversion efficiency โˆผ18 %) when submitted to an Air mass (AM) 1.5 solar spectrum [2]. The specific value of 1.5 for the Air mass is selected for standardization purposes, based on the analysis of solar irradiance data in the United States, and corresponds to a power of 1000 W/cm2 [3]. In the present work, a similar material a-Si0.5C0.5:H exhibiting 2.76 eV of energy bandgap generates a Jph of 17 mA/cm2 when submitted to the same light spectrum. This reflects an improvement in the use of a-SiC:H in PEC water splitting. Research on single thin film photoactive materials does not typically consider the role of the silicon substrate in the photoelectrochemical performance. In this sense, the photoelectrode is a system formed by a p-p, n-n or n-p structure, which depending on the depth of the space charge region may have an important impact on the photoelectrode performance. In this work, this substrate effect has been considered and studied. PEC performance of a-SiC:H is often limited by its non-ideal energy band-edge alignment to the H2O/O2 redox potential, thus limiting the oxygen evolution reaction (OER) and the whole water splitting process [4]. To overcome this downside, an external bias needs to be applied, contributing to counteract the overpotential required to trigger the direct water splitting reaction. The external bias also contributes to reduce overpotentials due to the presence of a surface SiO2 barrier layer and compensates interface charge carriers recombination as well. Previous studies have demonstrated that by removing the SiO2 native layer vii from a-SiC:H(i) surface, Jph values over 6 mA/cm2 can be achieved at a potential of -1.4 V vs. Ag/AgCl in contrast to values lower than < 4 mA/cm2 obtained without the oxide removal. In fact, the existence of surface states (SS) originated from the hydroxyl group termination on the oxide surface, form an electronic state that is typically located within the semiconductor bandgap. The theory that such states act as recombination centers for minority photo carriers, fits quite well with the assumption that surface recombination competes with charge transfer from the semiconductor band towards the electrolyte. Additionally, it has been reported that depending on the density and energetic position of SS, these can provide another favorable pathway for indirect charge transfer to the solution, competing with the undesirable recombination mechanism. Knowledge in this field is limitated to full-drift diffusion simulations in steady-state and dynamic regimes for photo-anodic currents in crystalline materials. In the current work, an experimental study has been carried out over an amorphous material (a-SiC:H) acting as photocathode for PEC water splitting. Thus, adding knowledge in this field. Attempts to understand the role of a-SiC defects in PEC water splitting performance have been carried out in 2009 by Simonds et al. [5]. As a result of these, defects density in the bulk of the a-SiC increases with carbon concentration, from โˆผ9 ร— 1016 cmโˆ’3 (6%C) to โˆผ8 ร— 1017 cmโˆ’3 (11%C), leading to a reduction of the PEC performance. On the other hand, defect densities in the SiC/SiO2 interface (SS) were approximated by Gaussian distributions with maximums of โˆผ2 ร— 1012 cmโˆ’2 ยท eVโˆ’1 (Ivanov et al. [6]). The latter finding was retrieved from Capacitance-Voltage (Cโˆ’V) measurements over metal-oxide-semiconductor (MOS) structures, and fit quite well with the SiC SS density distributions reported in this work. The current work consists in three parts. In the first part, Bandgap engineering of a-SiC:H thin films was carried out to assess the material light absorption without compromising its photoelectrochemical water splitting capabilities. The tailoring was performed by varying the hydrogen concentration in the semiconductor and by post-deposition isochronical annealing treatments from 200 to 700 โ—ฆC. By isochronical annealing, the same sample is submitted to the different temperature steps, from low to high temperature. After this analysis, the most suitable samples for water splitting application were evaluated as photocathodes in 1 M sulfuric acid under chopped light illumination. These a-SiC:H samples were doped with aluminum and deposited on different Silicon substrate conductivity types to assess the substrate influence in the a-SiC:H(Al) photocurrent response. This constitutes the second part or the work. Finally, in the third part, the role of SS in the photocathodic current for a-SiC:H(Al) absorber layers was experimentally analyzed. This analysis was based on steady-state and dynamic electrochemical models. Results concerning a-SiC:H(Al) photocathode stability under darkness and illumination conditions are also shown and discussed in this part. Concerning the findings and the novelty in this work, localized a-SiC:H(Al)/SiO2 SS would take part in a desirable mechanism of indirect electron charge transfer viii to the electrolyte, and thus, conduct hydrogen evolution reaction. Related to the SiO2 native layer, the evidence suggests that the SiO2 layer reduction during PEC tests triggers a favorable semiconductor-electrolyte interface. This interface exhibits less overpotential barriers which promotes photocurrent generation. A correlation exists between the retrieved SS density (NSS) and Urbach energy (EU) values. The EU is associated with disorder-induced electronic tail states or Urbach tails, which are localized states near the semiconductor band-edges. This correlation, as well as other a-SiC:H(Al)/SiO2 interface studies, support the reliability of our NSS calculations for the c-Si(p)/a-SiC:H(Al)/SiO2/electrolyte system. Finally, a charge transfer mechanism assisted by photogenerated minority carriers from the c-Si substrate has been also proposed in this wor

    Study of Cu-Exchanged CHA Catalysts for the Selective Catalytic Reduction (SCR) Reaction

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    Eliminating the harmful NOx, which is the major pollutant in the exhaust gas of diesel engines, has long been the pursue of scientists. Cu-chabazite (Cu-CHA) zeolites system developed in 2008 is shown to be an efficient and thermal stable catalyst in the deNOx NH3-SCR reaction and has received intense study since then. Aiming to further improve its catalytic activity, a wide range of characterization techniques has been developed and applied to study the well-defined structures and catalysis. Study of SCR reaction over the Cu-CHA catalysts demands the understanding of active Cu sites, for which loading-dependent behaviour is first studied with UV-Vis spectroscopy and ex-situ EPR spectroscopy together with the reaction evaluation. To further investigate different Cu species, the combination of H2-TPR, NH3-TPD and EPR spectroscopy were applied to quantify the Cu speciation in the catalysts, from which the sequential domination of 2AlCu, 1AlCu and CuO species with increasing Cu loadings was observed. Subsequent study of dehydration and hydrothermal aging processes with EPR also reveals the transformation of Cu species from 1AlCu to 2AlCu through the formation of hydrated complexes and the decomposition of CuOx clusters. On the other hand, the interaction between Cu-CHA catalysts and SCR reactants was studied with in situ FTIR and operando NEXAFS, showing the adsorption of NO and NH3 molecules respectively. Aiming to uncover the key species in the SCR reaction and reveal the origin of different reactivity for 1AlCu and 2AlCu sites, the samples with different Cu distribution was studied with operando X-ray spectroscopy under SCR conditions. With the combination of HERFD-XANES, vtc-XES and time-resolved XAS at transient states, key intermediate CuNOx species is observed to be preferentially formed on the 1AlCu sites, while a framework coordinated CuI(NH3)xOfw species is identified to be the real species causing NH3 inhibition effect, hindering the re-oxidation of CuI especially at 2AlCu sites

    Modulation of the Allosteric Communication between the Polo-Box Domain and the Catalytic Domain in Plk1 by Small Compounds

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    The Polo-like kinases (Plks) are an evolutionary conserved family of Ser/Thr protein kinases that possess, in addition to the classical kinase domain at the N-terminus, a C-terminal polo-box domain (PBD) that binds to phosphorylated proteins and modulates the kinase activity and its localization. Plk1, which regulates the formation of the mitotic spindle, has emerged as a validated drug target for the treatment of cancer, because it is required for numerous types of cancer cells but not for the cell division in noncancer cells. Here, we employed chemical biology methods to investigate the allosteric communication between the PBD and the catalytic domain of Plk1. We identified small compounds that bind to the catalytic domain and inhibit or enhance the interaction of Plk1 with the phosphorylated peptide PoloBoxtide in vitro. In cells, two new allosteric Plk1 inhibitors affected the proliferation of cancer cells in culture and the cell cycle but had distinct phenotypic effects on spindle formation. Both compounds inhibited Plk1 signaling, indicating that they specifically act on Plk1 in cultured cells.Fil: Raab, Monika. Goethe Universitat Frankfurt; AlemaniaFil: Sanhaji, Mourad. Goethe Universitat Frankfurt; AlemaniaFil: Pietsch, Larissa. German Cancer Research Center; Alemania. Goethe Universitat Frankfurt; AlemaniaFil: Bรฉquignon, Isabelle. Goethe Universitat Frankfurt; AlemaniaFil: Herbrand, Amanda K.. Goethe Universitat Frankfurt; AlemaniaFil: SรผรŸ, Evelyn. Goethe Universitat Frankfurt; AlemaniaFil: Gande, Santosh L.. German Cancer Research Center; Alemania. Goethe Universitat Frankfurt; AlemaniaFil: Caspar, Birgit. Goethe Universitat Frankfurt; AlemaniaFil: Kudlinzki, Denis. Goethe Universitat Frankfurt; Alemania. German Cancer Research Center; AlemaniaFil: Saxena, Krishna. Goethe Universitat Frankfurt; AlemaniaFil: Sreeramulu, Sridhar. Goethe Universitat Frankfurt; AlemaniaFil: Schwalbe, Harald. Goethe Universitat Frankfurt; Alemania. German Cancer Research Center; AlemaniaFil: Strebhardt, Klaus. Goethe Universitat Frankfurt; Alemania. German Cancer Research Center; AlemaniaFil: Biondi, Ricardo Miguel. German Cancer Research Center; Alemania. Goethe Universitat Frankfurt; Alemania. Consejo Nacional de Investigaciones Cientรญficas y Tรฉcnicas. Oficina de Coordinaciรณn Administrativa Parque Centenario. Instituto de Investigaciรณn en Biomedicina de Buenos Aires - Instituto Partner de la Sociedad Max Planck; Argentin
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