On the stability of carbon nanotube and titania nanowire based catalyst materials:from synthesis to applications

Abstract Degradation of the support and sintering of catalyst nanoparticles inherently leads to a loss of functionality of catalyst materials in converters and sensors. Malfunction in such devices may lead to serious economic and environmental damage. The quest for novel and sustainable catalyst materials with better durability is thus ongoing. In this thesis, one-dimensional nanomaterials such as carbon nanotubes and titanium dioxide nanowires are studied and compared to their conventional zero-dimensional counterparts in regard to their structural and functional stability. With the combination of several catalyst nanomaterials and supporting surfaces, aging properties of more than 70 different materials are assessed by the means of X-ray diffraction, transmission electron microscopy and energy-dispersive X-ray analyses. Although CNTs were shown to be thermally the most stable carbonaceous supports for metal nanoparticles, they are, similar to other carbon supports, more sensitive to high temperatures than metal oxide supports and can suffer deactivation by catalytic oxidation and gasification even at moderate temperatures. In addition, the irradiation of the samples with e-beams caused the most dramatic changes in CNT based materials, where nanosized deformities (voids, channels) were formed when either nanoparticles or defects were present. The prepared nanocompositions have been utilized successfully in three different applications including (i) synthesis of hydrogen from ethanol via a steam reforming reaction, (ii) hydrogenation of citral to form value added chemicals and (iii) the application of advanced electrode materials in electric double-layer capacitors. Both CNT and TiO₂ nanowire based nanomaterials were shown to outperform their conventional nano- and microparticle based counterparts in the studied catalytic reactions, i.e. in citral hydrogenation and steam reforming of ethanol, respectively. Furthermore, nanostructured CNTs obtained by catalytic partial oxidation of the material showed an increased specific surface area, which could be exploited in supercapacitor electrodes with enhanced specific capacitance.Tiivistelmä Katalyyttitukimateriaalin pilaantuminen ja katalyyttinanopartikkelien sintrautuminen johtavat siihen, että muuntajissa ja sensoreissa käytettävät katalyyttiset materiaalit eivät enää toimi, mikä voi aiheuttaa sekä vakavia taloudellisia haittoja että ympäristöhaittoja. Tämän vuoksi kehitetään uusia kestävämpiä katalyyttimateriaaleja. Tässä väitöskirjassa tutkittiin yksiulotteisia nanomateriaaleja, kuten hiilinanoputkia sekä titaanidioksidinanojohtimia ja verrattiin niiden rakenteellista ja toiminnallista stabiiliutta perinteisiin nollaulotteisiin vastineisiin. Erilaisten katalyyttinanomateriaalien ja tukimateriaalien yhdistelmien ikääntymistä arvioitiin röntgendiffraktion, läpäisyelektronimikroskopian ja energiadispersiivisen röntgenanalyysin avulla yli 70 erilaisesta näytteestä. Vaikka hiilinanoputket osoittautuivat termisesti stabiileimmaksi hiilipohjaiseksi tukimateriaaliksi metallinanopartikkeleille, ne ovat kuten kaikki hiilimateriaalit, metallioksiditukimateriaaleja herkempiä korkeille lämpötiloille. Hiilinanoputkipohjaiset katalyytit voivat deaktivoitua katalyyttisen hapettumisen tai kaasuuntumisen vuoksi jo kohtalaisissa lämpötiloissa. Lisäksi elektronisäteellä säteilytetyt nanopartikkelit tai pintavirheitä sisältävät hiilinanoputkipohjaiset katalyytit olivat tutkituista nanomateriaaleista herkimpiä muodostamaan nanorakenteita (koloja, kanavia). Valmistettuja nanokomposiitteja käytettiin onnistuneesti kolmessa eri sovelluksessa: i) vedyn valmistuksessa etanolista höyryreformointireaktiolla, ii) hienokemikaalien valmistuksessa sitraalin hydrauksella sekä iii) elektrodimateriaalina EDLC-kondensaattorissa. Sekä hiilinanoputki- sekä TiO₂-nanojohdinpohjaiset nanomateriaalit toimivat testatuissa katalyyttisissa reaktioissa (etanolin reformointi sekä sitraalin hydraus) paremmin kuin niiden perinteiset vastineet. Lisäksi superkondensaattorin ominaiskapasitanssia onnistuttiin nostamaan lisäämällä hiilinanoputkipohjaisen elektrodin ominaispinta-alaa katalyyttisella hapetusreaktiolla

2D tungsten chalcogenides:synthesis, properties and applications

Abstract Layered transition metal chalcogenides possess properties that not only open up broad fundamental scientific enquiries but also indicate that a myriad of applications can be developed by using these materials. This is also true for tungsten‐based chalcogenides which can provide an assortment of structural forms with different electronic flairs as well as chemical activity. Such emergence of tungsten based chalcogenides as advanced forms of materials lead several investigators to believe that a tremendous opportunity lies in understanding their fundamental properties, and by utilizing that knowledge the authors may create function specific materials through structural tailoring, defect engineering, chemical modifications as well as by combining them with other layered materials with complementary functionalities. Indeed several current scientific endeavors have indicated that an incredible potential for developing these materials for future applications development in key technology sectors such as energy, electronics, sensors, and catalysis are perhaps viable. This review article is an attempt to capture this essence by providing a summary of key scientific investigations related to various aspects of synthesis, characterization, modifications, and high value applications. Finally, some open questions and a discussion on imminent research needs and directions in developing tungsten based chalcogenide materials for future applications are presented

Synthesis and characterization of ceria-supported catalysts for carbon dioxide transformation to diethyl carbonate

Abstract The support materials Al₂O₃, SiO₂ and TiO₂ were modified with 16 wt% CeO₂, using two different preparation methods evaporation-impregnation and precipitation-deposition. The synthesized 16 wt% CeO₂-Al₂O₃, 16 wt% CeO₂-SiO₂ and 16 wt% CeO₂-TiO₂ materials were characterized by means of X-ray powder diffraction for the phase purity, scanning electron microscopy for the morphology, nitrogen physisorption to determine the specific surface area and X-ray photo electron spectroscopy for the oxidation state of the Ce in the TiO₂, Al₂O₃ and SiO₂ matrices. Transmission electron microscopy was used to study the particle size of CeO₂ whereas CO₂-temperature programmed desorption (TPD) was used to determine the basicity of ceria-modified TiO₂, Al₂O₃ and SiO₂ catalysts. Furthermore, the catalytic performance of the as prepared CeO₂-modified catalysts were compared in the synthesis of diethyl carbonate starting from ethanol and CO₂ using butylene oxide as the dehydrating agent. The physico-chemical characterization results were correlated with the catalytic activity results and discussed in detail

Portable cyber-physical system for indoor and outdoor gas sensing

Abstract A design, development and testing process for a cyber-physical system capable of versatile gas sensor measurement is described. Two approaches for the system are proposed; a stationary system for calibration and testing in laboratory environments and a portable system with wireless capability. The device utilizes a well-established Arduino microcontroller as well as a Raspberry Pi single board computer. The functionality is realized with C and Python programming languages. The operability is validated by system performance evaluation in the mixture of air and hydrogen gas, using both commercial and experimental Taguchi-type metal oxide semiconductor sensors. The experimental sensors are fabricated by inkjet printing platinum decorated tungsten oxide nanoparticles onto an electrode pattern on a silicon substrate which is then wire bonded to a chip carrier. The measurement platform demonstrated in our paper provides rapid prototyping capabilities for evaluating novel gas sensor materials in realistic measurement scenarios

Gas phase synthesis of isopropyl chloride from isopropanol and HCl over alumina and flexible 3-D carbon foam supported catalysts

Abstract Isopropyl chloride synthesis from isopropanol and HCl in gas phase over ZnCl₂ catalysts supported on Al₂O₃ as well as flexible carbon foam was studied in a continuous reactor. A series of catalytic materials were synthesised and characterised by BET, XPS, SEM, TEM, XRD and NH₃-TPD methods. Catalytic activity tests (product selectivity and conversion of reactants) were performed for all materials and optimal reaction conditions (temperature and feedstock flow rates) were found. The results indicate that the highest yield of isopropyl chloride was obtained over 5 wt.% ZnCl₂ on commercial Al₂O₃ (No. II) (95.3%). Determination of product mixture compositions and by-product identification were done using a GC-MS method. Carbon foam variant catalyst, 5 wt.% ZnCl₂/C, was found to perform best out of the carbon-supported materials, achieving ∼75% yield of isopropyl chloride. The kinetic model describing the process in a continuous packed bed reactor was proposed and kinetic parameters were calculated. The activation energy for the formation of isopropyl chloride reaction directly from isopropanol and HCl was found to be ∼58 kJ/mol