With the gradual depletion of the non-renewable fossil fuel resources and the emerging environmental concerns, the need of exploring renewable synthesis routes of our daily basic stocks is rising. Due to the large contribution to the global primary energy (up to 40% in some countries), biomass has recently been advocated to be one of the most promising alternatives for fossil fuel. This thesis focuses on the catalytic transformations of biomass or biomass derived molecules into valuable small alcohols such as methanol, ethanol, and propanol, which can be used as both fuel and chemical synthesis intermediates. Novel catalysts with high activity and selectivity toward target products are desperately required in the development of renewable chemical synthesis routes. In the past 200 years, platinum metal catalysts have been widely used in the industry. But nowadays, Pd is attracting increasing attentions due to (i) its similar physicochemical properties to those of Pt, (ii) its higher natural abundance than Pt. Alloying has been demonstrated as an effective method in enhancing the catalytic properties of noble metals. In this thesis, a new and facile method for the preparation of supported bimetallic NPs with tunable compositions is developed. Through the establishment of a type II hetero-junction in support, controllable amounts of metallic atoms can be derived from the reduction of the metal oxide support, with the assistance of a supported noble metal. A series of extremely small Pd-based bimetallic NPs with a variety of modifier atoms at tunable compositions, namely PdFe, PdCo, PdNi and PdZn, have been synthesized by this method. These novel bimetallic NPs are applied to the catalytic conversion of biomass or biomass derived molecules containing repeating vicinal diol units. It is demonstrated that the catalytic performance of Pd in bimetallic phase is governed by the d-band structure. The high degree of d-band filling and high d-band center position favour the selective C-O cleavage in hydrogenolysis of vicinal diol units. On the other hand, the selective C-C cleavage can be achieved by lowering the d-band filling of the Pd-based bimetallic NPs. The specificity of C-C bond rupture over that of C-O increases in order of PdZn < PdNi < PdCo < PdFe, with progressive d-band filling reduction, eventually reaches 95% in a series of vicinal diols hydrogenolysis. As a result, small alcohols are produced with high selectivity as the degradation products of biomass molecules when PdFe bimetallic NPs are employed as catalyst. Conversely, by incorporating Co atoms at high concentration, PdCo exhibits a high selectivity in breaking C-O bond of ethylene glycol due to the raised d-band center position and gives ethanol as the main product. Pd@Zn bimetallic NPs with an imperfect core(Pd)-shell(Zn) structure were used in a methanol synthesis route from biomass transformation via CO<sub>2</sub> hydrogenation (CO<sub>2</sub>/H<sub>2</sub> is produced from low temperature reforming of biomass resource). The Zn shell not only enhances the catalytic activity of Pd metal towards methanol synthesis, but also suppresses the reverse water gas shift (RWGS) reaction in which CO is produced as a by-product. Methanol can be produced as the main product over CO on the Zn rich Pd@Zn surface, even at low pressure. The methanol turnover frequency (TOF) on the exposed Pd site reaches 1.9 Ã10<sup>-1</sup> s<sup>-1</sup> with a selectivity of 70% at 2 MPa. The enhancement is attributed to the increasing d-band filling of Pd@Zn bimetallic NPs by the progressive decoration of Zn on Pd surface, which selectively stabilizes the precursor of methanol (HCOO) over that of CO (COOH). Also, the PdZn catalyst with high ability in dissociating H2 reduces the activation barrier for methanol synthesis. The results presented in this thesis, for the first time, signify the possibility of fine-tuning of product specificity of biomass conversion simply by rationally modifying the electronic properties of the Pd-based catalysts. More importantly, these catalysts will help to diversify the energy generation and relieve our dependence on fossil fuels.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:711825 |
| Date | January 2015 |
| Creators | Liao, Fenglin |
| Contributors | Tsang, S. C. Edman |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://ora.ox.ac.uk/objects/uuid:2fb03ce6-ba32-4102-96fc-f00fc7593bc0 |
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