Exsolved base metal catalyst systems with anchored nanoparticles for carbon monoxide (CO) and nitric oxides (NOₓ) oxidation

Abstract

Noble metals notably platinum (Pt), is a major element of heterogeneous catalysts, excel in catalysing an extensive number of important catalytic reactions in chemical and automotive industries. Since the increased use of these metals is severely limited because of their high cost and scarcity’s, there is therefore an urgent need for the search of alternative base metal catalysts that are cheaper and more widely available. This can only be practical if the main drawbacks of base metals such as the agglomeration of particles under high temperatures operational conditions and irreversible sulphur poisoning can be overcome, and their activity enhanced, such that they can directly replace Pt on a weight-to-weight basis. However, most previous studies have been restricted to low temperature reaction conditions and have not compared their activity directly to that of Pt, whether in terms of active sites or on a weight-to-weight basis. Moreover, most researchers have not investigated extensively the long-term stability of their base metal catalysts, since the longest was at most around 200 hours and at relatively low temperatures, for example at room temperature. It is proposed that long term stability can be achieved by producing uniformly distributed nano-sized socketed and strained base metal particles via the exsolution method. The main objective of this thesis is to produce exsolved base metals catalyst systems rivalling Pt on a weight-to-weight basis in two base reactions; CO and NO oxidation. NO oxidation was also chosen as our model reaction in this research since most Pt in the automotive industry are used in the lean NOx trap (LNT) or a combination of LNT and selective catalytic reduction (SCR), which demand the high conversion of NO to NO2 at low temperatures to work effectively. Initial screening experiments were performed to evaluate the potential CO oxidation activities and long-term stability at 520 °C of two different exsolved metal pellet systems namely lanthanum-doped ceria nickel titanates to exsolve nickel (Ni) metal (La0.8Ce0.1Ni0.4Ti0.6O3) and lanthanum-doped strontium iron nickel titanates to exsolve iron-nickel (FeNi) alloy (La0.5Sr0.4Fe0.1Ni0.1Ti0.6O3). Exsolved FeNi pellet system gives high and stable turnover frequencies (TOFs) of 103 s-1 at 520 °C for almost 170 hours, which confirms the potential of these stable exsolved metal systems for CO oxidation. Sixty exsolved metal powder systems with various metal formulations were produced to enable direct activity comparison to Pt on a weight-to-weight basis. Most exsolved metal systems displayed increasing CO2 production rates with increasing CO partial pressures (PCO) and reversible sulphur poisoning with exsolved CoNi powder system showing remarkable stability at 200 °C for 655 hours (one month). This exsolved CoNi system also showed enhanced activity for CO oxidation upon exposure to CO-rich environment, as a result of the restructuring of particles iv into metal oxide nanocubes anchored onto nanosockets within the support surface. The CO2 production rates of the activated exsolved CoNi powder system at 200 and 520 °C were 0.13 x 10-4 and 1.5 x 10-4 mol s-1 g-1 compared to its initial rate of around 0 (below the detected limit of 0.007 x10-4 mol s-1 g-1) and 0.8 x 10-4 mol s-1 g-1 prior to activation. These active spinel (CoNi)3O4 cubic structures were seen planted at an angle of ~55°, at the edge of an empty socket with mediocre features for CO oxidation, such as rich in Co2+ with exposed (100) planes that had only 44 cubes μm-2 compared to its initial 144 particles μm-2 particle population. Above 450 °C, the main active sites for CO oxidation were thought to be close to or at the metal-support interface of the exsolved CoNi systems. Comparable NO2 production rates to those of commercial Pt catalyst was achieved with only ± 5 % of difference at each measured point within the temperature range used (100-440 °C) over exsolved CoNi system by exploiting the effect of having two particle size ranges (10 and 30 nm). These results confirm the dual functionality of the activated exsolved CoNi system and its huge potential to be commercialised as an alternative catalyst to Pt in two oxidation reactions; CO and NO oxidation. In general, a simple procedure that induces high, long-lasting activity in a base metal catalyst, rivalling platinum for CO and NO oxidation on a weight-to-weight basis was demonstrated. The nature of this activation by tracking individual nanoparticles was successfully elucidated to link their microstructural evolution to their catalytic and kinetic behaviour. This research also illustrates new strategies for enhancing and tailoring the catalytic activity of base metal systems towards replacing platinum.