Browsing by Author "Zhang, Yan"
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Item Novel catalysts and photoelectrochemical system for solar fuel production(University of Delaware, 2016) Zhang, YanSolar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption spectroscopy (XAS). The photocatalytic activities of as-made nanoparticles were investigated using a well-studied visible light driven [Ru(bpy)3]2+-persulfate system. In both Clark electrode and reactor/gas chromatography (GC) systems, Mn-substituted Co3O 4 nanoparticles exhibited the highest turnover frequency (TOF) among all the three kinds of catalysts. The data presented in this paper suggest that the photocatalytic oxygen evolution activity of Co3O 4 spinel catalyst can be further enhanced by Mn3+ substitution at the octahedral sites. The second part of this piece of work was carried out to further investigate cobalt oxide based photocatalytic oxygen evolution catalyst. A new strategy was developed to synthesize nonsupported cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO 3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.0023 per second per cobalt in photocatalytic oxygen evolution reaction. X-ray absorption results suggested that a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen atoms and hydroxide groups in an octahedral arrangement to form 8 Co4O4 cubanes, may be responsible for the exceptionally high oxygen evolution catalysis activity. This thesis work is completed with the development of a photoanode-driven photoelectrochemical cell for CO2 reduction. A NiOx decorated Si photoanode and nanoporous Ag cathode were employed. With an external bias of 2.0 V, a current density at cathode of 10 mA/cm2 and Faradaic efficiency of 70% for CO2 to CO was achieved. Compared to a normal electrochemical cell, the photoelectrochemical cell saves 0.4 V electrical energy by absorbing photo-energy. In addition, post-test photoanodes were carefully characterized by SEM, XAS, and XPS analysis.Item Rhythmic RFID Authentication(IEEE/ACM Transactions on Networking, 2022-09-14) Li, Jiawei; Wang, Chuyu; Li, Ang; Han, Dianqi; Zhang, Yan; Zuo, Jinhang; Zhang, Rui; Xie, Lei; Zhang, YanchaoPassive RFID technology is widely used in user authentication and access control. We propose RF-Rhythm, a secure and usable two-factor RFID authentication system with strong resilience to lost/stolen/cloned RFID cards. In RF-Rhythm, each legitimate user performs a sequence of taps on his/her RFID card according to a self-chosen secret melody. Such rhythmic taps can induce phase changes in the backscattered signals, which the RFID reader can detect to recover the user’s tapping rhythm. In addition to verifying the RFID card’s identification information as usual, the backend server compares the extracted tapping rhythm with what it acquires in the user enrollment phase. The user passes authentication checks if and only if both verifications succeed. We also propose a novel phase-hopping protocol in which the RFID reader emits Continuous Wave (CW) with random phases for extracting the user’s secret tapping rhythm. Our protocol can prevent a capable adversary from extracting and then replaying a legitimate tapping rhythm from sniffed RFID signals. Comprehensive user experiments confirm the high security and usability of RF-Rhythm with false-positive and false-negative rates close to zero.Item SpecKriging: GNN-based Secure Cooperative Spectrum Sensing(IEEE Transactions on Wireless Communications, 2022-06-14) Zhang, Yan; Li, Ang; Li, Jiawei; Dianqi, Han; Li, Tao; Zhang, Rui; Zhang, YanchaoCooperative spectrum sensing (CSS) adopted by spectrum-sensing providers (SSPs) plays a key role for dynamic spectrum access and is essential for avoiding interference with licensed primary users (PUs). A typical SSP system consists of geographically distributed spectrum sensors which can be compromised to submit fake spectrum-sensing reports. In this paper, we propose SpecKriging, a new spatial-interpolation technique based on Inductive Graph Neural Network Kriging (IGNNK) for secure CSS. In SpecKriging, we first pretrain a graphical neural network (GNN) model with the historical sensing records of a few trusted anchor sensors. During system runtime, we use the trained model to evaluate the trustworthiness of non-anchor sensors’ data and also use them along with anchor sensors’ new data to retrain the model. SpecKriging outputs trustworthy sensor reports for spectrum-occupancy detection. To the best of our knowledge, SpecKriging is the first work that explores GNNs for trustworthy CSS and also incorporates the hardware heterogeneity of spectrum sensors. Extensive experiments confirm the high efficacy and efficiency of SpecKriging for trustworthy spectrum-occupancy detection even when malicious spectrum sensors constitute the majority.