Enhancing Hydrogen Production from the Photoreforming of Lignin.

Photoreforming of lignocellulose biomass is widely recognised as a challenging but key technology for producing value-added chemicals and renewable hydrogen (H2 ). In this study, H2 production from photoreforming of organosolv lignin in a neutral aqueous solution was studied over a 0.1 wt % Pt/TiO2 (P25) catalyst with ultraviolet A (UVA) light. The H2 production from the system employing the lignin (~4.8 µmol gcat -1 h-1 ) was comparable to that using hydroxylated/methoxylated aromatic model compounds (i. e., guaiacol and phenol, 4.8-6.6 µmol gcat -1 h-1 ), being significantly lower than that from photoreforming of cellulose (~62.8 µmol gcat -1 h-1 ). Photoreforming of phenol and reaction intermediates catechol, hydroquinone and benzoquinone were studied to probe the mechanism of phenol oxidation under anaerobic photoreforming conditions with strong adsorption and electron transfer reactions lowering H2 production from the intermediates relative to that from phenol. The issues associated with catalyst poisoning and low photoreforming activity of lignins demonstrated in this paper have been mitigated by implementing a process by which the catalyst was cycled through anaerobic and aerobic conditions. This strategy enabled the periodic regeneration of the photocatalyst resulting in a threefold enhancement in H2 production from the photoreforming of lignin.

Mechanistic Study of Glucose Photoreforming over TiO2-Based Catalysts for H2 Production.

Glucose is a key intermediate in cellulose photoreforming for H2 production. This work presents a mechanistic investigation of glucose photoreforming over TiO2 and Pt/m-TiO2 catalysts. Analysis of the intermediates formed in the process confirmed the α-scission mechanism of glucose oxidation forming arabinose (Cn-1 sugar) and formic acid in the initial oxidation step. The selectivity to sugar products and formic acid differed over Pt/TiO2 and TiO2, with Pt/TiO2 showing the lower selectivity to formic acid due to enhanced adsorption/conversion of formic acid over Pt/TiO2. In situ ATR-IR spectroscopy of glucose photoreforming showed the presence of molecular formic acid and formate on the surface of both catalysts at low glucose conversions, suggesting that formic acid oxidation could dominate surface reactions in glucose photoreforming. Further in situ ATR-IR of formic acid photoreforming showed Pt-TiO2 interfacial sites to be key for formic acid oxidation as TiO2 was unable to convert adsorbed formic acid/formate. Isotopic studies of the photoreforming of formic acid in D2O (with different concentrations) showed that the source of the protons (to form H2 at Pt sites) was determined by the relative surface coverage of adsorbed water and formic acid.

Fracking wastewater treatment: Catalytic performance and life cycle environmental impacts of cerium-based mixed oxide catalysts for catalytic wet oxidation of organic compounds.

Water scarcity and the consequent increase of freshwater prices are a cause for concern in regions where shale gas is being extracted via hydraulic fracturing. Wastewater treatment methods aimed at reuse/recycle of fracking wastewater can help reduce water stress of the fracking process. Accordingly, this study assessed the catalytic performance and life cycle environmental impacts of cerium-based mixed oxide catalysts for catalytic wet oxidation (CWO) of organic contaminants, in order to investigate their potential as catalysts for fracking wastewater treatment. For these purposes, MnCeOx and CuCeOx were tested for phenol removal in the presence of concentrated NaCl (200 g L-1), which represented a synthetic fracking wastewater. Removal of phenol in pure ("phenolic") water without NaCl was also considered for comparison. Complete (100 %) phenol and a 94 % total organic carbon (TOC) removal were achieved in both the phenolic and fracking wastewaters by utilising MnCeOx (5 g L-1) and insignificant metal leaching was observed. However, a much lower activity was observed when the same amount of CuCeOx was utilised: 23.3 % and 20.5 % for phenol and TOC removals, respectively, in the phenolic, and 69.1 % and 63 % in the fracking wastewater. Furthermore, severe copper leaching from CuCeOx was observed during stability tests conducted in the fracking wastewater. A life cycle assessment (LCA) study carried out as part of this work showed that the production of MnCeOx had 12-98 % lower impacts than CuCeOx due to the higher impacts of copper than manganese precursors. Furthermore, the environmental impacts of CWO were found to be 94-99 % lower than those of ozonation due to lower energy and material requirements. Overall, the results of this study suggest that the adoption of catalytic treatment would improve both the efficiency and the environmental sustainability of both the fracking wastewater treatment and the fracking process as a whole.

Combined Superbase Ionic Liquid Approach to Separate CO2 from Flue Gas.

Superbase ionic liquids (ILs) with a trihexyltetradecylphosphonium cation and a benzimidazolide ([P66614][Benzim]) or tetrazolide ([P66614][Tetz]) anion were investigated in a dual-IL system allowing the selective capture and separation of CO2 and SO2, respectively, under realistic gas concentrations. The results show that [P66614][Tetz] is capable of efficiently capturing SO2 in preference to CO2 and thus, in a stepwise separation process, protects [P66614][Benzim] from the negative effects of the highly acidic contaminant. This results in [P66614][Benzim] maintaining >53% of its original CO2 uptake capacity after 30 absorption/desorption cycles in comparison to the 89% decrease observed after 11 cycles when [P66614][Tetz] was not present. Characterization of the ILs post exposure revealed that small amounts of SO2 were irreversibly absorbed to the [Benzim]- anion responsible for the decrease in CO2 capacity. While optimization of this dual-IL system is required, this feasibility study demonstrates that [P66614][Tetz] is a suitable sorbent for reversibly capturing SO2 and significantly extending the lifetime of [P66614][Benzim] for CO2 uptake.

High-Ionic-Strength Wastewater Treatment via Catalytic Wet Oxidation over a MnCeO x Catalyst.

Catalytic wastewater treatment has rarely been applied to treat high-ionic-strength wastewater (HISWW) as it contains large amounts of catalyst poisons (e.g., Cl-). This work investigates the catalytic wet oxidation (CWO) of phenol over a MnCeO x catalyst in the presence of high NaCl concentrations where the combination of MnCeO x and NaCl promoted the CWO of phenol. Specifically, in the presence of NaCl at a concentration of 200 g L-1 and MnCeO x at a concentration of 1.0 g L-1, phenol (initially 1.0 g L-1) and total organic carbon (TOC) conversions were ∼98 and 85%, respectively, after a 24 h reaction. Conversely, under the same reaction conditions without NaCl, the catalytic system only achieved phenol and TOC conversions of ∼41 and 27%, respectively. In situ Attenuated Total Reflection infrared spectroscopy identified the nature of the strongly adsorbed carbon deposits with quinone/acid species found on Ce sites and phenolate species on Mn sites in the single oxides and on MnCeO x . The presence of high concentrations of NaCl reduced the carbon deposition over the catalyst, promoting surface oxidation of the hydrocarbon and reoxidation of the catalyst, resulting in enhanced mineralization. Moreover, the used MnCeO x catalyst in the salt water system was efficiently regenerated via a salt water wash under the reaction conditions, showing the great potential of MnCeO x in practical HISWW treatment.

Photocatalytic Reforming of Biomass: What Role Will the Technology Play in Future Energy Systems.

Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as 'hydrogen' and 'visible' becoming prominent research topics. There are likely two primary drivers behind this, the first of which is that biomass represents a more sustainable photocatalytic feedstock for reforming to value-added products and energy. The second is the transition towards achieving net zero emission targets, which has increased focus on the development of technologies that could play a role in future energy systems. Therefore, this review provides a perspective on not only the current state of the research but also a future outlook on the potential roadmap for photocatalytic reforming of biomass. Producing energy via photocatalytic biomass reforming is very desirable due to the ambient operating conditions and potential to utilise renewable energy (e.g., solar) with a wide variety of biomass resources. As both interest and development within this field continues to grow, however, there are challenges being identified that are paramount to further advancement. In reviewing both the literature and trajectory of the field, research priorities can be identified and utilised to facilitate fundamental research alongside whole systems evaluation. Moreover, this would underpin the enhancement of photocatalytic technology with a view towards improving the technology readiness level and promoting engagement between academia and industry.

Effect of Ball-Milling Pretreatment of Cellulose on Its Photoreforming for H2 Production.

Photoreforming of cellulose is a promising route for sustainable H2 production. Herein, ball-milling (BM, with varied treatment times of 0.5-24 h) was employed to pretreat microcrystalline cellulose (MCC) to improve its activity in photoreforming over a Pt/TiO2 catalyst. It was found that BM treatment reduced the particle size, crystallinity index (CrI), and degree of polymerization (DP) of MCC significantly, as well as produced amorphous celluloses (with >2 h treatment time). Amorphous cellulose water-induced recrystallization to cellulose II (as evidenced by X-ray diffraction (XRD) and solid-state NMR analysis) was observed in aqueous media. Findings of the work showed that the BM treatment was a simple and effective pretreatment strategy to improve photoreforming of MCC for H2 production, mainly due to the decreased particle size and, specifically in aqueous media, the formation of the cellulose II phase from the recrystallization of amorphous cellulose, the extent of which correlates well with the activity in photoreforming.

Combined Experimental and Theoretical Study of the Competitive Absorption of CO2 and NO2 by a Superbase Ionic Liquid.

A superbase ionic liquid (IL), trihexyltetradecylphosphonium benzimidazolide ([P66614][Benzim]), is investigated for the capture of CO2 in the presence of NO2 impurities. The effect of the waste gas stream contaminant on the ability of the IL to absorb simultaneously CO2 is demonstrated using novel measurement techniques, including a mass spectrometry breakthrough method and in situ infrared spectroscopy. The findings show that the presence of an industrially relevant concentration of NO2 in a combined feed with CO2 has the effect of reducing the capacity of the IL to absorb CO2 efficiently by ∼60% after 10 absorption-desorption cycles. This finding is supported by physical property analysis (viscosity, 1H and 13C NMR, and X-ray photoelectron spectroscopy) and spectroscopic infrared characterization, in addition to density functional theory (DFT) calculations, to determine the structure of the IL-NO2 complex. The results are presented in comparison with another flue gas component, NO, demonstrating that the absorption of NO2 is more favorable, thereby hindering the ability of the IL to absorb CO2. Significantly, this work aids understanding of the effects that individual components of flue gas have on CO2 capture sorbents, through studying a contaminant that has received limited interest previously.

Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts.

Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5.

The mono(µ-oxo) dicopper cores present in the pores of Cu-ZSM-5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM-5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1-2 wt % SiO2, IR studies showed a 64 % relative reduction in external copper species and temperature-programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu-ZSM-5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol.

Quantitative measurement of the reduction of platinum(IV) complexes using X-ray absorption near-edge spectroscopy (XANES).

The platinum(II) drugs cisplatin, carboplatin and oxaliplatin are usefully employed against a range of malignancies, but toxicities and resistance have spurred the search for improved analogs. This has included investigation of the platinum(IV) oxidation state, which provides greater kinetic inertness. It is generally accepted that Pt(IV) complexes must be reduced to Pt(II) for activation. As such, the ability to monitor reduction of Pt(IV) complexes is critical to guiding the design of candidates, and providing mechanistic understanding. Here we report in full that the white line height of X-ray absorption near-edge spectra (XANES) of Pt complexes, normalized to the post-edge minima, can be used to quantitatively determine the proportion of each oxidation state in a mixture. A series of Pt(IV) complexes based on the Pt(II) complexes cisplatin and transplatin were prepared with chlorido, acetato or hydroxido axial ligands, and studies into their reduction potential and cytotoxicity against A2780 human ovarian cancer cells were performed, demonstrating the relationship between reduction potential and cytotoxicity. Analysis of white line height demonstrated a clear and consistent difference between Pt(II) (1.52 ± 0.05) and Pt(IV) (2.43 ± 0.19) complexes. Reduction of Pt(IV) complexes over time in cell growth media and A2780 cells was observed by XANES, and shown to correspond with their reduction potentials and cytotoxicities. We propose that this method is useful for monitoring reduction of metal-based drug candidates in complex biological systems.

Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms.

DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO(2). It was found that a highly hydroxylated surface of blank SnO(2) reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO(2) the sensor signal maximum towards H(2) in dry air (R(0)/R(g)) is observed at approximately 345 degrees C, and towards water, at approximately 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO(2) is unchanged. The interaction of hydrogen with the catalyst doped SnO(2) occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H(2) by a factor of 1000.

Heterogeneous chemistry of toluene, kerosene and diesel soots.

Soot samples as potential mimics of atmospheric aerosols have been produced from the combustion of toluene, kerosene and diesel in order to compare the nature of soot produced from a simpler material, toluene, with soots from the fuels kerosene and diesel. Characterisation of the soots using elemental analysis, infrared spectroscopy, solvent extraction, thermal desorption and electron microscopy techniques before and after reaction with ozone allows assessment of the reactivity of soots from these different fuels. Despite the production of toluene and kerosene soots from identical combustion conditions, strong differences in structure and reactivity are observed in terms of their reaction with ozone. However, toluene soot is a much better mimic of diesel soot. It is proposed that the differing reactivities of the soots is related to the nature of the organic carbon and structure of the elemental carbon which vary with soots from the different fuels.