In this work, a Pt catalyst supported on an equimolar Al 2 O 3 –CeO 2 binary oxide (Pt–Al–Ce) was prepared and applied in photo-thermo-chemical dry reforming of methane (DRM) driven by concentrated solar irradiation. It was found that the Pt–Al–Ce catalyst showed good stability in DRM reactions and significant enhancements in H 2 and CO production rates compared with Pt/CeO 2 (Pt–Ce) and Pt/Al 2 O 3 (Pt–Al) catalysts. At a reaction temperature of 700 °C under 30-sun equivalent solar irradiation, the Pt–Al–Ce catalyst exhibits a stable DRM catalytic performance at a H 2 production rate of 657 mmol g −1 h −1 and a CO production rate of 666 mmol g −1 h −1 , with the H 2 /CO ratio almost equal to unity. These production rates and the H 2 /CO ratio were significantly higher than those obtained in the dark at the same temperature. The light irradiation was found to induce photocatalytic activities on Pt–Al–Ce and reduce the reaction activation energy. In situ diffuse reflectance infrared Fourier transform spectroscopy ( in situ DRIFTS) was applied to identify the active intermediates in the photo-thermo-chemical DRM process, which were bidentate/monodentate carbonate, absorbed CO on Pt, and formate.more »
Integrating photocatalysis and thermocatalysis to enable efficient CO2 reforming of methane on Pt supported CeO2 with Zn doping and atomic layer deposited MgO overcoating
CO2 reforming or dry reforming of methane (DRM) produces syngas with a low carbon footprint, but the efficiency and stability of DRM remains a challenge. Herein, we report an efficient photo-thermo-chemical DRM (PTC-DRM) process on a Pt supported CeO2 catalyst with Zn doping and surface atomic layer deposition (ALD)-enabled MgO overcoating using concentrated sunlight as the energy input. Under 30 suns irradiation at 600 °C, high syngas production rates of 356 and 516 mmol g−1 h−1 for H2 and CO are achieved, which are more than 9 and 3 times larger than those obtained in the thermally driven DRM. Moreover, the light illumination stabilizes the dry reforming process without deactivation, which results from the in situ generation of oxygen vacancy on CeO2 by photo-induced electrons that enables stable CO2 thermo-activation. The ALD coating also reduces surface charge recombination through passivating surface states, thereby enhancing photocatalytic activity.
- Award ID(s):
- 1924574
- Publication Date:
- NSF-PAR ID:
- 10158267
- Journal Name:
- Applied catalysis
- Volume:
- 260
- Page Range or eLocation-ID:
- 118189
- ISSN:
- 0166-9834
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Integration of carbon dioxide capture from flue gas with dry reforming of CH 4 represents an attractive approach for CO 2 utilization. The selection of a suitable bifunctional material serving as a catalyst/sorbent is the key. This paper reports Ni decorated and CeO x -stabilized SrO (SrCe 0.5 Ni 0.5 ) as a multi-functional, phase transition catalytic sorbent material. The effect of CeO x on the morphology, structure, decarbonation reactivity, and cycling stability of the catalytic sorbent was determined with TEM-EDX, XRD, in situ XRD, CH 4 -TPR and TGA. Cyclic process tests were conducted in a packed bed reactor. The results indicate that large Ni clusters were present on the surface of the SrNi sorbent, and the addition of CeO 2 promoted even distribution of Ni on the surface. Moreover, the Ce–Sr interaction promoted a complex carbonation/decarbonation phase-transition, i.e. SrCO 3 + CeO 2 ↔ Sr 2 CeO 4 + CO 2 as opposed to the conventional, simple carbonation/decarbonation cycles ( e.g. SrCO 3 ↔ SrO + CO 2 ). This double replacement crystalline phase transition mechanism not only adjusts the carbonation/calcination thermodynamics to facilitate SrCO 3 decomposition at relatively low temperatures but also inhibits sorbent sintering. As amore »
-
Abstract. Dry deposition is a key process for surface ozone(O3) removal. Stomatal uptake is a major component of O3 drydeposition, which is parameterized differently in current land surfacemodels and chemical transport models. We developed and used a standaloneterrestrial biosphere model, driven by a unified set of prescribedmeteorology, to evaluate two widely used dry deposition modeling frameworks,Wesely (1989) and Zhang et al. (2003), with different configurations ofstomatal resistance: (1) the default multiplicative method in the Weselyscheme (W89) and Zhang et al. (2003) scheme (Z03), (2) the traditionalphotosynthesis-based Farquhar–Ball–Berry (FBB) stomatal algorithm, and (3) theMedlyn stomatal algorithm (MED) based on optimization theory. We found thatusing the FBB stomatal approach that captures ecophysiological responses toenvironmental factors, especially to water stress, can generally improve thesimulated dry deposition velocities compared with multiplicative schemes.The MED stomatal approach produces higher stomatal conductance than FBB andis likely to overestimate dry deposition velocities for major vegetationtypes, but its performance is greatly improved when spatially varying slopeparameters based on annual mean precipitation are used. Large discrepancieswere also found in stomatal responses to rising CO2 levels from 390to 550 ppm: the multiplicative stomatal method with an empirical CO2response function produces reduction (−35 %) in global stomatalconductance on average much larger than that with the photosynthesis-basedstomatal method (−14 %–19 %). Ourmore »
-
Chemical Looping Reaction is a key strategy to achieve both emission reduction and carbon utilization while producing various value-added chemicals, through redox reactions. Here we study the effect of nanoshape ceria supported Ru catalysts for plasma assisted Chemical Looping Reforming reduction step coupled with water splitting oxidation step reactions in the temperature range 150 ⁰C to 400 ⁰C at 1 atm pressure. The oxygen carrier/catalyst combination materials used are Ru/CeO2 nanorods (NR), Ru/CeO2 nanocubes (NC), Ru/SiO2 nanospheres (NS), and Ni-based perovskite mixed with CeO2. NRs and NCs showed the best catalytic performance followed by Ni-based perovskite and NS. Differences in the selectivity and reactivity for the NRs and NCs were noticed. The NCs showed slightly higher selectivity towards H2 formation during reduction step and lesser carbon deposition. From the analysis of data and literature, it is proposed that the spillover of species such as H adatoms and CHx radicals after activation at Ru sites into the CeO2 supports and lattice O mobility may be slightly faster in the case of NCs. During the oxidation step, the NR and NC materials showed increased H2 production by a factor of more than 4 when compared to Ni based perovskite material.
-
Steam reforming of methane (SRM) is one of the most important industrial processes, which produces 95% of hydrogen used in the USA. However, SRM is an endothermic reaction, which requires a high energy input and a high reaction temperature (>800 °C) for the current process. Furthermore, its products must be subjected to a water–gas shift (WGS) process. A photocatalytic process is expected to solve the energy issue and to eliminate the necessity of WGS for SRM. However, the hydrogen yield from the current photocatalytic steam reforming of methane (PSRM) is very low (μmol h −1 g −1 level), which is far below industrial interest. This work demonstrates that a Pt/blackTiO 2 catalyst dispersed on a light-diffuse-reflection-surface is excellent for efficient visible-light PSRM. Under visible light illumination on the catalyst by filtering UV light from AM 1.5G sunlight, CH 4 and H 2 O were directly converted into H 2 and CO 2 without WGS, leading to a high H 2 yield of 185 mmol h −1 g −1 with a quantum efficiency of 60% at 500 °C. The yield is 3 orders of magnitude larger than the reported values, which can be attributed to the synergistic effect between potential andmore »