Renewable hydrogen to recycle CO2 to methanol

The balance of the natural carbon cycle disrupted by the large consumption of fossil fuels, in particular coal producing electricity, may in principle be restored by using renewable hydrogen. This paper considers the opportunity to recycle the CO₂ produced burning fossil fuels with oxy-fuel combustion using renewable hydrogen as the second feed-stock. The product, methanol, is a transportation fuel having significant advantages over not only over hydrogen, but also gasoline, permitting much better fuel conversion efficiencies than gasoline thanks to the larger heat of vaporisation and the largest resistance to knock that make this fuel the best option for small, high power density, turbocharged, directly injected stoichiometric engines.     

Pd-Gardenia-TiO2 as a photocatalyst for H2 evolution from pure water

The photocatalytic activity for H₂ evolution from pure water over Pd loaded TiO₂ prepared by gardenia extract (Pd-Gardenia-TiO₂) is systematically investigated. The as-prepared photocatalysts are characterized by X-ray diffraction, high resolution transmission electron microscopy, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. Gardenia extract functions as reducing and stabilizing agents simultaneously. The mean size of the as-prepared Pd nanoparticles is in the range of 2.3 ± 0.5 nm based on TEM images. The Pd-Gardenia-TiO₂ catalyst exhibits good photocatalytic activity for H₂ evolution (93 μmol · h⁻¹ · g⁻¹), which is much higher than that of Pd photodeposited on TiO₂. Possible factors for its photocatalytic activity from pure water are also investigated.     

Controllable proton and CO2 photoreduction over Cu2O with various morphologies

Simultaneous photocatalytic reduction of water to H₂ and CO₂ to CO was observed over Cu₂O photocatalyst under both full arc and visible light irradiation (>420 nm). It was found that the photocatalytic reduction preference shifts from H₂ (water splitting) to CO (CO₂ reduction) by controlling the exposed facets of Cu₂O. More interestingly, the low index facets of Cu₂O exhibit higher activity for CO₂ photoreduction than high index facets, which is different from the widely-reported in which the facets with high Miller indices would show higher photoactivity. Improved CO conversion yield could be further achieved by coupling the Cu₂O with RuO_x to form a heterojunction which slows down fast charge recombination and relatively stabilises the Cu₂O photocatalyst. The RuO_x amount was also optimised to maximise the junction's photoactivity.     

Role of CO2 in the CH4 oxidation and H2 formation during fuel-rich combustion in O2/CO2 environments

The effect of CO₂ reactivity on CH₄ oxidation and H₂ formation in fuel-rich O₂/CO₂ combustion where the concentrations of reactants were high was studied by a CH₄ flat flame experiment, detailed chemical analysis, and a pulverized coal combustion experiment. In the CH₄ flat flame experiment, the residual CH₄ and formed H₂ in fuel-rich O₂/CO₂ combustion were significantly lower than those formed in air combustion, whereas the amount of CO formed in fuel-rich O₂/CO₂ combustion was noticeably higher than that in air. In addition to this experiment, calculations were performed using CHEMKIN-PRO. They generally agreed with the experimental results and showed that CO₂ reactivity, mainly expressed by the reaction CO₂ + H → CO + OH (R1), caused the differences between air and O₂/CO₂ combustion under fuel-rich condition. R1 was able to advance without oxygen. And, OH radicals were more active than H radicals in the hydrocarbon oxidation in the specific temperature range. It was shown that the role of CO₂ was to advance CH₄ oxidation during fuel-rich O₂/CO₂ combustion. Under fuel-rich combustion, H₂ was mainly produced when the hydrocarbon reacted with H radicals. However, the hydrocarbon also reacted with the OH radicals, leading to H₂O production. In fact, these hydrocarbon reactions were competitive. With increasing H/OH ratio, H₂ formed more easily; however, CO₂ reactivity reduced the H/OH ratio by converting H to OH. Moreover, the OH radicals reacted with H₂, whereas the H radicals did not reduce H₂. It was shown that OH radicals formed by CO₂ reactivity were not suitable for H₂ formation. As for pulverized coal combustion, the tendencies of CH₄, CO, and H₂ formation in pulverized coal combustion were almost the same as those in the CH₄ flat flame.     

Preparation of ZnIn2S4/fluoropolymer fiber composites and its photocatalytic H2 evolution from splitting of water using Xe lamp irradiation

This paper focuses on the preparation of ZnIn₂S₄/fluoropolymer fiber composites and their performance for H₂ evolution from splitting of water using Xe lamp irradiation. Hexafluorobutyl acrylate-co-methacrylic acid (poly(HFBA-co-MAA)) is synthesized by a solution polymerization. Next, the fluoropolymer fibers, which have around 100 nm in average diameter, of poly(HFBA-co-MAA) and polyvinylidene fluoride (PVDF) mixtures are obtained by electrospinning. Then, zinc and indium ions are introduced onto the fiber surface by coordinating with carboxyls of MAA. After that, sulfide ions are incorporated to react with zinc and indium ions by a hydrothermal synthesis. Thus, ZnIn₂S₄ particles of around 800 nm in average size, are obtained and well loaded on the fiber surface. The absorption edge of ZnIn₂S₄/fluoropolymer fiber composites is at 510 nm within the visible-light region. Photocatalytic H₂ evolution from water was investigated using Xe lamp. It was found that the average rate of H₂ evolution of ZnIn₂S₄ powders gradually decreased, while the average rate of H₂ evolution of ZnIn₂S₄/fluoropolymer fiber composites increased from the first to the third run. The average rate of H₂ evolution using the ZnIn₂S₄/fluoropolymer fiber composites as the catalyst achieved 9.1 mL/h in the third run.     

Sorbent enhanced hydrogen production from steam gasification of coal integrated with CO2 capture

In this work, CO₂ capture and H₂ production during the steam gasification of coal integrated with CO₂ capture sorbent were investigated using a horizontal fixed bed reactor at atmospheric pressure. Four different temperatures (650, 675, 700, and 750 °C) and three sorbent-to-carbon ratios ([Ca]/[C] = 0, 1, 2) were studied. In the absence of sorbent, the maximum molar fraction of H₂ (64.6%) and conversion of coal (71.3%) were exhibited at the highest temperature (750 °C). The experimental results verified that the presence of sorbent in the steam gasification of coal enhanced the molar fraction of H₂ to more than 80%, with almost all CO₂ was fixed into the sorbent structure, and carbon monoxide (CO) was converted to H₂ and CO₂ through the water gas shift reaction. The steam gasification of coal integrated with CO₂ capture largely depended on the reaction temperature and exhibited optimal conditions at 675 °C. The maximum molar fraction of H₂ (81.7%) and minimum CO₂ concentration (almost 0%) were obtained at 675 °C and a sorbent-to-carbon ratio of 2.     

Metal-organic frameworks for CO2 photoreduction

Metal-organic frameworks (MOFs) have attracted much attention because of their large surface areas, tunable structures, and potential applications in many areas. In recent years, MOFs have shown much promise in CO₂ photoreduction. This review summarized recent research progresses in MOF-based photocatalysts for photocatalytic reduction of CO₂. Besides, it discussed strategies in rational design of MOF-based photocatalysts (functionalized pristine MOFs, MOF-photosensitizer, MOF-semiconductor, MOF-metal, and MOF-carbon materials composites) with enhanced performance on CO₂ reduction. Moreover, it explored challenges and outlook on using MOF-based photocatalysts for CO₂ reduction.     

Highly efficient TiO2 nanotube photocatalyst for simultaneous hydrogen production and copper removal from water

1-D mesoporous TiO₂ nanotube (TNT) with large BET surface area was successfully synthesized by a hydrothermal-calcination process, and employed for simultaneous photocatalytic H₂ production and Cu²⁺ removal from water. Cu²⁺, across a wide concentration range of 8-800 ppm, was removed rapidly from water under irradiation. The removed Cu²⁺ then combined with TNT to produce efficient Cu incorporated TNT (Cu-TNT) photocatalyst for H₂ production. Average H₂ generation rate recorded across a 4 h reaction was between 15.7 and 40.2 mmol h⁻¹ g⁻¹_catalyst, depending on initial Cu²⁺/Ti ratio in solution, which was optimized at 10 atom%. In addition, reduction process of Cu²⁺ was also a critical factor in governing H₂ evolution. In comparison with P25, its large surface area and 1-D tubular structure endowed TNT with higher photocatalytic activity in both Cu²⁺ removal and H₂ production.     

Production of hydrogen through the carbonation–calcination reaction applied to CH4/CO2 mixtures

The production of hydrogen combined with carbon capture represents a possible option for reducing CO₂ emissions in atmosphere and anthropogenic greenhouse effect. Nowadays the worldwide hydrogen production is based mainly on natural gas reforming, but the attention of the scientific community is focused also on other gas mixtures with significant methane content. In particular mixtures constituted mainly by methane and carbon dioxide are extensively used in energy conversion applications, as they include land-fill gas, digester gas and natural gas. The present paper addresses the development of an innovative system for hydrogen production and CO₂ capture starting from these mixtures. The plant is based on steam methane reforming, coupled with the carbonation and calcination reactions for CO₂ absorption and desorption, respectively. A thermodynamic approach is proposed to investigate the plant performance in relation to the CH₄ content in the feeding gas. The results suggest that, in order to optimize the hydrogen purity and the efficiency, two different methodologies can be adopted involving both the system layout and operating parameters. In particular such methodologies are suitable for a methane content, respectively, higher and lower than 65%.     

Enhanced hydrogen generation from methanol aqueous solutions over Pt/MoO3/TiO2 under ultraviolet light

The photocatalytic activity in hydrogen production from methanol reforming can be significantly enhanced by Pt/MoO₃/TiO₂ photocatalysts. Compared with Pt/P25, the photocatalytic activity of optimized Pt/MoO₃/TiO₂ shows an evolution rate of 169 μmol/h/g of hydrogen, which is almost two times higher than that of Pt/P25. XRD and Raman spectra show that MoO₃ are formed on the surface of TiO₂. It is found that with the bulk MoO₃ just formed, the catalyst shows the highest activity due to a large amount of heterojunctions and the high crystallinity of MoO₃. The HRTEM image showed a close contact between MoO₃ and TiO₂. It is proposed that the Z-scheme type of heterojunction between MoO₃ and TiO₂ is responsible for the improved photocatalytic activity. The heterojunction structure of MoO₃/TiO₂ does not only promote the charge separation, but also separates the reaction sites, where the oxidation (mainly on MoO₃) and reduction (on TiO₂) reactions occurred.     

Hydrogen production from coal gasification for effective downstream CO2 capture

The coal gasification process is used in commercial production of synthetic gas as a means toward clean use of coal. The conversion of solid coal into a gaseous phase creates opportunities to produce more energy forms than electricity (which is the case in coal combustion systems) and to separate CO₂ in an effective manner for sequestration. The current work compares the energy and exergy efficiencies of an integrated coal-gasification combined-cycle power generation system with that of coal gasification-based hydrogen production system which uses water-gas shift and membrane reactors. Results suggest that the syngas-to-hydrogen (H₂) system offers 35% higher energy and 17% higher exergy efficiencies than the syngas-to-electricity (IGCC) system. The specific CO₂ emission from the hydrogen system was 5% lower than IGCC system. The Brayton cycle in the IGCC system draws much nitrogen after combustion along with CO₂. Thus CO₂ capture and compression become difficult due to the large volume of gases involved, unlike the hydrogen system which has 80% less nitrogen in its exhaust stream. The extra electrical power consumption for compressing the exhaust gases to store CO₂ is above 70% for the IGCC system but is only 4.5% for the H₂ system. Overall the syngas-to-hydrogen system appears advantageous to the IGCC system based on the current analysis.     

Integrated fossil fuel and solar thermal systems for hydrogen production and CO2 mitigation

In most current fossil-based hydrogen production methods, the thermal energy required by the endothermic processes of hydrogen production cycles is supplied by the combustion of a portion of the same fossil fuel feedstock. This increases the fossil fuel consumption and greenhouse gas emissions. This paper analyzes the thermodynamics of several typical fossil fuel-based hydrogen production methods such as steam methane reforming, coal gasification, methane dissociation, and off-gas reforming, to quantify the potential savings of fossil fuels and CO₂ emissions associated with the thermal energy requirement. Then matching the heat quality and quantity by solar thermal energy for different processes is examined. It is concluded that steam generation and superheating by solar energy for the supply of gaseous reactants to the hydrogen production cycles is particularly attractive due to the engineering maturity and simplicity. It is also concluded that steam-methane reforming may have fewer engineering challenges because of its single-phase reaction, if the endothermic reaction enthalpy of syngas production step (CO and H₂) of coal gasification and steam methane reforming is provided by solar thermal energy. Various solar thermal energy based reactors are discussed for different types of production cycles as well.     

Photocatalytic activity of Ag–TiO2-graphene ternary nanocomposites and application in hydrogen evolution by water splitting

TiO₂-graphene (P25-GR, PG) nanocomposite was fabricated with P25 and graphite oxide through a hydrothermal method, and then Ag nanoparticles (Ag NPs) was assembled in P25-GR (Ag-P25-GR, APG) under microwave-assisted chemical reduction. The prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscopy (TEM), photoluminescence spectrum (PL), UV–vis absorption spectrum (UV–vis) and Raman spectrum, respectively. The results showed that Ag NPs were well dispersed on the surface of PG with metallic state. The ternary Ag-P25-GR (APG) nanocomposites possessed the extended light absorption range and more efficient charge separation properties compared to binary P25-GR (PG). Methylene blue photodegradation experiment proved that surface plasmon resonance (SPR) phenomenon had an effect on photoreaction efficiency. The corresponding hydrogen evolution rate of APG prepared with 0.002 M AgNO₃ solution was 7.6 times than pure P25 and 2.7 times than PG in the test condition. The improved photocatalytic performance can be attributed to the presence of GR and SPR effect, leading to the longer lifetime of photo-generated electron–hole pairs and faster interfacial charge transfer rate. This work indicates that the photoactivity of ternary GR-based nanocomposites is superior to the binary one. We expected our work could give a new train of thought on exploration of GR-based nanocomposites.     

TiO2 nanosheets loaded with Cu: A low-cost efficient photocatalytic system for hydrogen evolution from water

Rutile TiO₂ nanosheets were prepared by a simple solvothermal process, and Cu was loaded on the surface of TiO₂ nanosheets using the in situ photo-deposition method. Meanwhile, photocatalytic H₂ evolution from water over the as-prepared TiO₂ nanosheets loaded with Cu was explored using methanol as a sacrificial reagent. The results indicate that the TiO₂ nanosheets loaded with Cu is an efficient photocatalyst under UV irradiation. During the first 5 h, a rate of H₂ evolution of approximately 22.1 mmol g⁻¹ h⁻¹ was achieved under optimal conditions. Furthermore, for practical purposes, the photocatalytic hydrogen evolution was studied as a function of content of Cu, pH of solution, concentration of methanol and dosage of photocatalyst, respectively. At last, the photocatalytic mechanism was preliminarily discussed.     

Visible-light sensitive hydrogen evolution photocatalyst ZnRh2O4

We investigated the ability of the oxide ZnRh₂O₄ to serve as a solar H₂-evolution photocatalyst due to the predicted potential of its conduction band bottom, which may allow thermodynamically favorable H₂ evolution in spite of its small band-gap of 1.2 eV. ZnRh₂O₄ produced H₂ in the presence of HCHO, but only scarcely in the presence of CH₃OH, indicating that the potential of the valence band top of ZnRh₂O₄ lies at ∼0.1 V (vs. SHE). Thus, the conduction band bottom potential (∼−1.1 V) lies much more negative than the potential of H⁺/H₂, allowing thermodynamically favorable H₂ evolution. In addition, the irradiated-light-wavelength dependence of the quantum efficiency (QE) for H₂ evolution was consistent with the solar spectrum, and the QE was quite high (∼27%), even at a wavelength of 770 ± 25 nm. Taken together, our findings indicate that ZnRh₂O₄ can utilize solar light effectively, not only the entire range of UV and visible light, but is also sensitive to infrared light.     

Photocatalytic hydrogen evolution over CuCrO2

We have been studying the technical feasibility of a photochemical H₂ evolution based on a dispersion of CuCrO₂ powder in aqueous electrolytes containing various reducing agents (S²⁻, and ). The title oxide combines a fair resistance to corrosion with an optimal band gap E_g of 1.32 eV. The intercalation of a small amount of oxygen should be accompanied by a partial oxidation of Cu⁺ into Cu²⁺ implying a p-type semiconductivity. The S²⁻ oxidation inhibits the photocorrosion and the H₂ evolution increases parallel to polysulfides formation. Most of H₂ is produced when p-CuCrO₂ is connected to n-Cu₂O formed in situ. H₂ liberation proceeds mostly on CuCrO₂ while the oxidation of S²⁻ takes place over Cu₂O surface and the hetero system Cu₂O/CuCrO₂ is optimized with respect to some physical parameters. The photoactivity is dependent on preparation conditions and lowering the synthesis temperature through nitrate route leads to an increase in specific surface area S_sp. The photoelectrochemical H₂ production is a multistep process where the rate determining step is the arrival of electrons at the interface because of their low mobility. Prolonged irradiation (>80 min) leads to a pronounced decrease of the photoactivity; the tendency toward saturation is due to the undesired back reduction of polysulfides in a closed system and to their strong absorption in the visible region (λ_max = 520 nm).     

Promotion of CO2 methanation activity and CH4 selectivity at low temperatures over Ru/CeO2/Al2O3 catalysts

The effect of CeO₂ loading amount of Ru/CeO₂/Al₂O₃ on CO₂ methanation activity and CH₄ selectivity was studied. The CO₂ reaction rate was increased by adding CeO₂ to Ru/Al₂O₃, and the order of CO₂ reaction rate at 250 °C is Ru/30%CeO₂/Al₂O₃ > Ru/60%CeO₂/Al₂O₃ > Ru/CeO₂ > Ru/Al₂O₃. With a decrease in CeO₂ loading of Ru/CeO₂/Al₂O₃ from 98% to 30%, partial reduction of CeO₂ surface was promoted and the specific surface area was enlarged. Furthermore, it was observed using FTIR technique that intermediates of CO₂ methanation, such as formate and carbonate species, reacted with H₂ faster over Ru/30%CeO₂/Al₂O₃ and Ru/CeO₂ than over Ru/Al₂O₃. These could result in the high CO₂ reaction rate over CeO₂-containing catalysts. As for the selectivity to CH₄, Ru/30%CeO₂/Al₂O₃ exhibited high CH₄ selectivity compared with Ru/CeO₂, due to prompt CO conversion into CH₄ over Ru/30%CeO₂/Al₂O₃.     

TiO2 nanotubes incorporated with CdS for photocatalytic hydrogen production from splitting water under visible light irradiation

The CdS/TiO₂ composites were synthesized using titanate nanotubes (TiO₂NTs) with different pore diameters as the precursor by simple ion change and followed by sulfurization process at a moderate temperature. Some of results obtained from XRD, TEM, BET, UV–vis and PL analysis confirmed that cadmium sulfide nanoparticles (CdSNPs) incorporated into the titanium dioxide nanotubes. The photocatalytic production of H₂ was remarkably enhanced when CdS nanoparticles was incorporated into TiO₂NTs. The apparent quantum yield for hydrogen production reached about 43.4% under visible light around λ = 420 nm. The high activity might be attributed to the following reasons: (1) the quantum size effect and homogeneous distribution of CdSNPs; (2) the synergetic effects between CdS particles and TiO₂NTs, viz., the potential gradient at the interface between CdSNPs and TiO₂NTs.     

Electrospun Pt/TiO2 hybrid nanofibers for visible-light-driven H2 evolution

One-dimensional (1D) Pt/TiO₂ hybrid nanofibers (HNFs) with different concentrations of Pt were fabricated by a facile two-step synthesis route combining an electrospinning technique and calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) results showed that the Pt nanoparticles (NPs) with the size of 5–10 nm were well dispersed in the TiO₂ nanofibers (NFs). Further investigations from the UV–Vis diffuse reflectance (DR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that some Pt ions were incorporated into the TiO₂ lattice as Pt⁴⁺ state, which contributed to the visible light absorption of TiO₂ NFs. Meanwhile, the Pt²⁺ ions existing on the surface of Pt NPs resulted in the formation of Pt–O–Ti bond at Pt NPs/TiO₂ NFs interfaces that might serve as an effective channel for improving the charge transfer. The as-electrospun Pt/TiO₂ HNFs exhibited remarkable activities for photocatalytic H₂ evolution under visible light irradiation in the presence of l-ascorbic acid as the sacrificial agent. In particular, the optimal HNFs containing 1.0 at% Pt showed the H₂ evolution rate of 2.91 μmol h⁻¹ and apparent quantum efficiency of 0.04% at 420 nm by using only 5 mg of photocatalysts. The higher photocatalytic activity could be ascribed to the appropriate amount of Pt ions doping and excellent electron-sink effect of Pt NPs co-catalysts.     

Liquid CO2 droplet extraction from gases

Efficient mechanical separation of CO₂ from combustion effluent affects the utilization potential of high CO₂ producers such as coal. Novel mechanical separations of condensing CO₂ from gas flows need to be able to capture the small condensed droplets below the cyclone cut-off limit of 20 μm. We describe the thermodynamics, the energy costs and droplet formation of CO₂ phase separation from combustion effluent and natural gas. We report the first measurements of condensing CO₂ droplet sizes from gas. This shows that application of homogeneous condensation of CO₂ yields much smaller droplets in flue gas (N₂/CO₂) than from contaminated natural gas (CH₄/CO₂). These small droplets can only be efficiently removed at high throughputs using the novel centrifugal method we describe. Such mechanical separations are preferable to the current standard chemical methods because of the much lower environmental footprint.