Effect of Gas Composition on Temperature and CO2 Conversion in a Gliding Arc Plasmatron reactor: Insights for Post-Plasma Catalysis from Experiments and Computation.

Plasma-based CO2 conversion has attracted increasing interest. However, to understand the impact of plasma operation on post-plasma processes, we studied the effect of adding N2, N2/CH4 and N2/CH4/H2O to a CO2 gliding arc plasmatron (GAP) to obtain valuable insights into their impact on exhaust stream composition and temperature, which will serve as feed gas and heat for post-plasma catalysis (PPC). Adding N2 improves the CO2 conversion from 4 % to 13 %, and CH4 addition further promotes it to 44 %, and even to 61 % at lower gas flow rate (6 L/min), allowing a higher yield of CO and hydrogen for PPC. The addition of H2O, however, reduces the CO2 conversion from 55 % to 22 %, but it also lowers the energy cost, from 5.8 to 3 kJ/L. Regarding the temperature at 4.9 cm post-plasma, N2 addition increases the temperature, while the CO2/CH4 ratio has no significant effect on temperature. We also calculated the temperature distribution with computational fluid dynamics simulations. The obtained temperature profiles (both experimental and calculated) show a decreasing trend with distance to the exhaust and provide insights in where to position a PPC bed.

Controlling Pt nanoparticle sintering by sub-monolayer MgO ALD thin films.

Metal nanoparticle (NP) sintering is a major cause of catalyst deactivation, as NP growth reduces the surface area available for reaction. A promising route to halt sintering is to deposit a protective overcoat on the catalyst surface, followed by annealing to generate overlayer porosity for gas transport to the NPs. Yet, such a combined deposition-annealing approach lacks structural control over the cracked protection layer and the number of NP surface atoms available for reaction. Herein, we exploit the tailoring capabilities of atomic layer deposition (ALD) to deposit MgO overcoats on archetypal Pt NP catalysts with thicknesses ranging from sub-monolayers to nm-range thin films. Two different ALD processes are studied for the growth of MgO overcoats on Pt NPs anchored on a SiO2 support, using Mg(EtCp)2 and H2O, and Mg(TMHD)2 and O3, respectively. Spectroscopic ellipsometry and X-ray photoelectron spectroscopy measurements reveal significant growth on both SiO2 and Pt for the former process, while the latter exhibits a drastically lower growth per cycle with an initial chemical selectivity towards Pt. These differences in MgO growth characteristics have implications for the availability of uncoated Pt surface atoms at different stages of the ALD process, as probed by low energy ion scattering, and for the sintering behavior during O2 annealing, as monitored in situ with grazing incidence small angle X-ray scattering (in situ GISAXS). The Mg(TMHD)2-O3 ALD process enables exquisite coverage control allowing a balance between physically blocking the Pt surface to prevent sintering and keeping Pt surface atoms free for reaction. This approach avoids the need for post-annealing, hence also safeguarding the structural integrity of the as-deposited overcoat.

Efficient removal and transformation of Cr(VI) from alkaline wastewater to form a ferrochromium spinel multiphase via a modified ferrite process.

Chromium-containing wastewater causes serious environmental pollution due to the harmfulness of Cr(VI). The ferrite process is typically used to treat chromium-containing wastewater and recycle the valuable chromium metal. However, the current ferrite process is unable to fully transform Cr(VI) into chromium ferrite under mild reaction conditions. This paper proposes a novel ferrite process to treat chromium-containing wastewater and recover valuable chromium metal. The process combines FeSO4 reduction and hydrothermal treatment to remove Cr(VI) and form chromium ferrite composites. The Cr(VI) concentration in the wastewater was reduced from 1040 mg L-1 to 0.035 mg L-1, and the Cr(VI) leaching toxicity of the precipitate was 0.21 mg L-1 under optimal hydrothermal conditions. The precipitate consisted of micron-sized ferrochromium spinel multiphase with polyhedral structure. The mechanism of Cr(VI) removal involved three steps: 1) partial oxidation of FeSO4 to Fe(III) hydroxide and oxy-hydroxide; 2) reduction of Cr(VI) by FeSO4 to Cr(III) and Fe(III) precipitates; 3) transformation and growth of the precipitates into chromium ferrite composites. This process meets the release standards of industrial wastewater and hazardous waste and can improve the efficiency of the ferrite process for toxic heavy metal removal.

Does CO2 Oxidize Ni Catalysts? A Quick X-ray Absorption Spectroscopy Answer.

MgAl2O4-supported Ni materials are highly active and cost-effective CO2 conversion catalysts, yet their oxidation by CO2 remains dubious. Herein, NiO/MgAl2O4, prepared via colloidal synthesis (10 wt % Ni) to limit size distribution, or wet impregnation (5, 10, 20, and 40 wt % Ni), and bare, i.e., unsupported, NiO are examined in H2 reduction and CO2 oxidation, using thermal conductivity detector-based measurements and in situ quick X-ray absorption spectroscopy, analyzed via multivariate curve resolution-alternating least-squares. Ni reoxidation does not occur for bare Ni but is observed solely on supported materials. Only samples with the smallest particle sizes get fully reoxidized. The Ni-MgAl2O4 interface, exhibiting metal-support interactions, activates CO2 and channels oxygen into the reduced lattice. Oxygen diffuses inward, away from the interface, oxidizing Ni entirely or partially, depending on the particle size in the applied oxidation time frame. This work provides evidence for Ni oxidation by CO2 and explores the conditions of its occurrence and the importance of metal-support effects.

Sufficient extraction of Cr from chromium ore processing residue (COPR) by selective Mg removal.

Chromium ore processing residue (COPR) is a hazardous waste generated during the production of chromate. Currently, approximately 10% of Cr2O3 cannot be extracted after chromite sodium roasting and remains in COPR, wasting valuable Cr resources. In this study, Mg was selectively removed by using (NH4)2SO4 roasting in combination with H2SO4 leaching. The results showed that the selective removal of 79.55% Mg from COPR could be achieved under the optimum (NH4)2SO4 roasting conditions (80 mmol (NH4)2SO4, 800 °C, 2 h). During the subsequent sodium roasting and acid leaching stages, the Cr extraction rate was 84.63% for the COPR direct roasting and 95.39% for the Mg removal residue roasting. The increased Cr extraction efficiency is attributed to the transformation of Mg-rich spinel and diopside (the Mg & Cr coexisting phases) in COPR converted into easily extractable (Fe,Cr)2O3 and Cr2O3 after the Mg treatment. This study investigated that the phase transformation of the Cr host phases is crucial for the sufficient extraction of Cr and provides inspiration for the development of efficient and practical Cr extraction techniques. Moreover, the method can be extended to the effective extraction of Cr from other Cr-containing wastes.

Aligning time-resolved kinetics (TAP) and surface spectroscopy (AP-XPS) for a more comprehensive understanding of ALD-derived 2D and 3D model catalysts.

The spectro-kinetic characterization of complex catalytic materials, i.e. relating the observed reaction kinetics to spectroscopic descriptors of the catalyst state, presents a fundamental challenge with a potentially significant impact on various chemical technologies. We propose to reconcile the kinetic characteristics available from temporal analysis of products (TAP) pulse-response kinetic experiments with the spectroscopic data available from ambient pressure X-ray photoelectron spectroscopy (AP-XPS), using atomic layer deposition (ALD) to synthesize multicomponent model surfaces on 2D and 3D supports. The accumulated surface exposure to a key reactant (total number of collisions) is used as a common scale within which the results from the two techniques can be rigorously compared for microscopically-equivalent surfaces. This approach is illustrated by proof-of-principle TAP and AP-XPS experiments with PtIn/MgO/SiO2 catalysts for alkane dehydrogenation at 800 K. Similarly to industrially-relevant Pt-based bimetallic catalysts on high-surface area supports, the initial period of coke accumulation on the surface resulted in gradually decreased conversion and increased selectivity towards propylene. We were able to monitor the process of coke deposition with both AP-XPS and TAP. The evolution of the C 1s photoelectron spectra is aligned on the common exposure scale with the evolution of the coke amounts deposited per Pt site during a multi-pulse TAP experiment. Moreover, TAP provided quantitative kinetic descriptors of propane consumption and product mean residence time within this common exposure scale. The challenges and opportunities presented by this novel tandem methodology are discussed in the context of catalysis research.

Spherical core-shell alumina support particles for model platinum catalysts.

γ- and δ-alumina are popular catalyst support materials. Using a hydrothermal synthesis method starting from aluminum nitrate and urea in diluted solution, spherical core-shell particles with a uniform particle size of about 1 µm were synthesized. Upon calcination at 1000 °C, the particles adopted a core-shell structure with a γ-alumina core and δ-alumina shell as evidenced by 2D and 3D electron microscopy and 27Al magic angle spinning nuclear magnetic resonance spectroscopy. The spherical alumina particles were loaded with Pt nanoparticles with an average size below 1 nm using the strong electrostatic adsorption method. Electron microscopy and energy dispersive X-ray spectroscopy revealed a homogeneous platinum dispersion over the alumina surface. These platinum loaded alumina spheres were used as a model catalyst for bifunctional catalysis. Physical mixtures of Pt/alumina spheres and spherical zeolite particles are equivalent to catalysts with platinum deposited on the zeolite itself facilitating the investigation of the catalyst components individually. The spherical alumina particles are very convenient supports for obtaining a homogeneous distribution of highly dispersed platinum nanoparticles. Obtaining such a small Pt particle size is challenging on other support materials such as zeolites. The here reported and well-characterized Pt/alumina spheres can be combined with any zeolite and used as a bifunctional model catalyst. This is an interesting strategy for the examination of the acid catalytic function without the interference of the supported platinum metal on the investigated acid material.

Designing Nanoparticles and Nanoalloys for Gas-Phase Catalysis with Controlled Surface Reactivity Using Colloidal Synthesis and Atomic Layer Deposition.

Supported nanoparticles are commonly applied in heterogeneous catalysis. The catalytic performance of these solid catalysts is, for a given support, dependent on the nanoparticle size, shape, and composition, thus necessitating synthesis techniques that allow for preparing these materials with fine control over those properties. Such control can be exploited to deconvolute their effects on the catalyst's performance, which is the basis for knowledge-driven catalyst design. In this regard, bottom-up synthesis procedures based on colloidal chemistry or atomic layer deposition (ALD) have proven successful in achieving the desired level of control for a variety of fundamental studies. This review aims to give an account of recent progress made in the two aforementioned synthesis techniques for the application of controlled catalytic materials in gas-phase catalysis. For each technique, the focus goes to mono- and bimetallic materials, as well as to recent efforts in enhancing their performance by embedding colloidal templates in porous oxide phases or by the deposition of oxide overlayers via ALD. As a recent extension to the latter, the concept of area-selective ALD for advanced atomic-scale catalyst design is discussed.

Formation and Functioning of Bimetallic Nanocatalysts: The Power of X-ray Probes.

Bimetallic nanocatalysts are key enablers of current chemical technologies, including car exhaust converters and fuel cells, and play a crucial role in industry to promote a wide range of chemical reactions. However, owing to significant characterization challenges, insights in the dynamic phenomena that shape and change the working state of the catalyst await further refinement. Herein, we discuss the atomic-scale processes leading to mono- and bimetallic nanoparticle formation and highlight the dynamics and kinetics of lifetime changes in bimetallic catalysts with showcase examples for Pt-based systems. We discuss how in situ and operando X-ray spectroscopy, scattering, and diffraction can be used as a complementary toolbox to interrogate the working principles of today's and tomorrow's bimetallic nanocatalysts.

Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X-ray Absorption Spectroscopy.

Alloyed metal nanocatalysts are of environmental and economic importance in a plethora of chemical technologies. During the catalyst lifetime, supported alloy nanoparticles undergo dynamic changes which are well-recognized but still poorly understood. High-temperature O2 -H2 redox cycling was applied to mimic the lifetime changes in model Pt13 In9 nanocatalysts, while monitoring the induced changes by in situ quick X-ray absorption spectroscopy with one-second resolution. The different reaction steps involved in repeated Pt13 In9 segregation-alloying are identified and kinetically characterized at the single-cycle level. Over longer time scales, sintering phenomena are substantiated and the intraparticle structure is revealed throughout the catalyst lifetime. The in situ time-resolved observation of the dynamic habits of alloyed nanoparticles and their kinetic description can impact catalysis and other fields involving (bi)metallic nanoalloys.

Advanced Chemical Looping Materials for CO2 Utilization: A Review.

Combining chemical looping with a traditional fuel conversion process yields a promising technology for low-CO2-emission energy production. Bridged by the cyclic transformation of a looping material (CO2 carrier or oxygen carrier), a chemical looping process is divided into two spatially or temporally separated half-cycles. Firstly, the oxygen carrier material is reduced by fuel, producing power or chemicals. Then, the material is regenerated by an oxidizer. In chemical looping combustion, a separation-ready CO2 stream is produced, which significantly improves the CO2 capture efficiency. In chemical looping reforming, CO2 can be used as an oxidizer, resulting in a novel approach for efficient CO2 utilization through reduction to CO. Recently, the novel process of catalyst-assisted chemical looping was proposed, aiming at maximized CO2 utilization via the achievement of deep reduction of the oxygen carrier in the first half-cycle. It makes use of a bifunctional looping material that combines both catalytic function for efficient fuel conversion and oxygen storage function for redox cycling. For all of these chemical looping technologies, the choice of looping materials is crucial for their industrial application. Therefore, current research is focused on the development of a suitable looping material, which is required to have high redox activity and stability, and good economic and environmental performance. In this review, a series of commonly used metal oxide-based materials are firstly compared as looping material from an industrial-application perspective. The recent advances in the enhancement of the activity and stability of looping materials are discussed. The focus then proceeds to new findings in the development of the bifunctional looping materials employed in the emerging catalyst-assisted chemical looping technology. Among these, the design of core-shell structured Ni-Fe bifunctional nanomaterials shows great potential for catalyst-assisted chemical looping.

Ultrafast and Stable CO2 Capture Using Alkali Metal Salt-Promoted MgO-CaCO3 Sorbents.

As a potential candidate for precombustion CO2 capture at intermediate temperatures (200-400 °C), MgO-based sorbents usually suffer from low kinetics and poor cyclic stability. Herein, a general and facile approach is proposed for the fabrication of high-performance MgO-based sorbents via incorporation of CaCO3 into MgO followed by deposition of a mixed alkali metal salt (AMS). The AMS-promoted MgO-CaCO3 sorbents are capable of adsorbing CO2 at an ultrafast rate, high capacity, and good stability. The CO2 uptake of sorbent can reach as high as above 0.5 gCO2 gsorbent-1 after only 5 min of sorption at 350 °C, accounting for vast majority of the total uptake. In addition, the sorbents are very stable even under severe but more realistic conditions (desorption in CO2 at 500 °C), where the CO2 uptake of the best sorbent is stabilized at 0.58 gCO2 gsorbent-1 in 20 consecutive cycles. The excellent CO2 capture performance of the sorbent is mainly due to the promoting effect of molten AMS, the rapid formation of CaMg(CO3)2, and the plate-like structure of sorbent. The exceptional ultrafast rate and the good stability of the AMS-promoted MgO-CaCO3 sorbents promise high potential for practical applications, such as precombustion CO2 capture from integrated gasification combined cycle plants and sorption-enhanced water gas shift process.

Fe-Based Nano-Materials in Catalysis.

The role of iron in view of its further utilization in chemical processes is presented, based on current knowledge of its properties. The addition of iron to a catalyst provides redox functionality, enhancing its resistance to carbon deposition. FeOx species can be formed in the presence of an oxidizing agent, such as CO2, H2O or O2, during reaction, which can further react via a redox mechanism with the carbon deposits. This can be exploited in the synthesis of active and stable catalysts for several processes, such as syngas and chemicals production, catalytic oxidation in exhaust converters, etc. Iron is considered an important promoter or co-catalyst, due to its high availability and low toxicity that can enhance the overall catalytic performance. However, its operation is more subtle and diverse than first sight reveals. Hence, iron and its oxides start to become a hot topic for more scientists and their findings are most promising. The scope of this article is to provide a review on iron/iron-oxide containing catalytic systems, including experimental and theoretical evidence, highlighting their properties mainly in view of syngas production, chemical looping, methane decomposition for carbon nanotubes production and propane dehydrogenation, over the last decade. The main focus goes to Fe-containing nano-alloys and specifically to the Fe⁻Ni nano-alloy, which is a very versatile material.

Super-dry reforming of methane intensifies CO2 utilization via Le Chatelier's principle.

Efficient CO2 transformation from a waste product to a carbon source for chemicals and fuels will require reaction conditions that effect its reduction. We developed a "super-dry" CH4 reforming reaction for enhanced CO production from CH4 and CO2 We used Ni/MgAl2O4 as a CH4-reforming catalyst, Fe2O3/MgAl2O4 as a solid oxygen carrier, and CaO/Al2O3 as a CO2 sorbent. The isothermal coupling of these three different processes resulted in higher CO production as compared with that of conventional dry reforming, by avoiding back reactions with water. The reduction of iron oxide was intensified through CH4 conversion to syngas over Ni and CO2 extraction and storage as CaCO3 CO2 is then used for iron reoxidation and CO production, exploiting equilibrium shifts effected with inert gas sweeping (Le Chatelier's principle). Super-dry reforming uses up to three CO2 molecules per CH4 and offers a high CO space-time yield of 7.5 millimole CO per second per kilogram of iron at 1023 kelvin.

Insights into the Reaction Mechanism of Ethanol Conversion into Hydrocarbons on H-ZSM-5.

Ethanol dehydration to ethene is mechanistically decoupled from the production of higher hydrocarbons due to complete surface coverage by adsorbed ethanol and diethyl ether (DEE). The production of C3+ hydrocarbons was found to be unaffected by water present in the reaction mixture. Three routes for the production of C3+ hydrocarbons are identified: the dimerization of ethene to butene and two routes involving two different types of surface species categorized as aliphatic and aromatic. Evidence for the different types of species involved in the production of higher hydrocarbons is obtained via isotopic labeling, continuous flow and transient experiments complemented by UV/Vis characterization of the catalyst and ab initio microkinetic modeling.

Atomic Layer Deposition Route To Tailor Nanoalloys of Noble and Non-noble Metals.

Since their early discovery, bimetallic nanoparticles have revolutionized various fields, including nanomagnetism and optics as well as heterogeneous catalysis. Knowledge buildup in the past decades has witnessed that the nanoparticle size and composition strongly impact the nanoparticle's properties and performance. Yet, conventional synthesis strategies lack proper control over the nanoparticle morphology and composition. Recently, atomically precise synthesis of bimetallic nanoparticles has been achieved by atomic layer deposition (ALD), alleviating particle size and compositional nonuniformities. However, this bimetal ALD strategy applies to noble metals only, a small niche within the extensive class of bimetallic alloys. We report an ALD-based approach for the tailored synthesis of bimetallic nanoparticles containing both noble and non-noble metals, here exemplified for Pt-In. First, a Pt/In2O3 bilayer is deposited by ALD, yielding precisely defined Pt-In nanoparticles after high-temperature H2 reduction. The nanoparticles' In content can be accurately controlled over the whole compositional range, and the particle size can be tuned from micrometers down to the nanometer scale. The size and compositional flexibility provided by this ALD-approach will trigger the fabrication of fully tailored bimetallic nanomaterials, including superior nanocatalysts.

The role of hydrogen during Pt-Ga nanocatalyst formation.

Hydrogen plays an essential role during the in situ assembly of tailored catalytic materials, and serves as key ingredient in multifarious chemical reactions promoted by these catalysts. Despite intensive debate for several decades, the existence and nature of hydrogen-involved mechanisms - such as hydrogen-spillover, surface migration - have not been unambiguously proven and elucidated up to date. Here, Pt-Ga alloy formation is used as a probe reaction to study the behavior and atomic transport of H and Ga, starting from Pt nanoparticles on hydrotalcite-derived Mg(Ga)(Al)Ox supports. In situ XANES spectroscopy, time-resolved TAP kinetic experiments, HAADF-STEM imaging and EDX mapping are combined to probe Pt, Ga and H in a series of H2 reduction experiments up to 650 °C. Mg(Ga)(Al)Ox by itself dissociates hydrogen, but these dissociated hydrogen species do not induce significant reduction of Ga(3+) cations in the support. Only in the presence of Pt, partial reduction of Ga(3+) into Ga(δ+) is observed, suggesting that different reaction mechanisms dominate for Pt- and Mg(Ga)(Al)Ox-dissociated hydrogen species. This partial reduction of Ga(3+) is made possible by Pt-dissociated H species which spillover onto non-reducible Mg(Al)Ox or partially reducible Mg(Ga)(Al)Ox and undergo long-range transport over the support surface. Moderately mobile Ga(δ+)Ox migrates towards Pt clusters, where Ga(δ+) is only fully reduced to Ga(0) on condition of immediate stabilization inside Pt-Ga alloyed nanoparticles.

Advanced elemental characterization during Pt-In catalyst formation by wavelet transformed X-ray absorption spectroscopy.

Complementary to conventional X-ray absorption near edge structure (XANES) and Fourier transformed (FT) extended X-ray absorption fine structure (EXAFS) analysis, the systematic application of wavelet transformed (WT) XAS is shown to disclose the physicochemical mechanisms governing Pt-In catalyst formation. The simultaneous k- and R-space resolution of the WT XAS signal allows for the efficient allocation of the elemental nature to each R-space peak. Because of its elemental discrimination capacity, the technique delivers structural models which can subsequently serve as an input for quantitative FT EXAFS modeling. The advantages and limitations of applying WT XAS are demonstrated (1) before and (2) after calcination to 650 °C of a Pt(acac)2 impregnated Mg(In)(Al)Ox support and (3) after subsequent H2 reduction to 650 °C. Combined XANES, FT, and WT XAS analysis shows that the acac ligands of the Pt precursor decompose during calcination, leading to atomically dispersed Pt(4+) cations on the Mg(In)(Al)Ox support. H2 reduction treatment eventually results in the formation of 1.5 nm Pt-In alloyed nanoparticles. Widespread use and systematic application of wavelet-based XAS can potentially reveal in greater detail the intricate mechanisms involved in catalysis, chemistry, and related fields.

TAP study of toluene total oxidation over a Co3O4/La-CeO2 catalyst with an application as a washcoat of cordierite honeycomb monoliths.

The total oxidation of toluene was studied over a Co3O4/La-CeO2 catalyst in a Temporal Analysis of Products (TAP) set-up in the temperature range 713 K to 873 K in the presence and absence of dioxygen. It has been demonstrated that the reaction proceeds via a Mars-van Krevelen mechanism. The reaction rate increased 8.4 times if both toluene and dioxygen were present in the feed. The partial reaction order with respect to O2 diminished from 0.9 to 0.6 with an increase in temperature from 763 to 873 K. Adsorbed oxygen species with a lifetime of ∼8 s have been found on a catalyst fully oxidized by dioxygen. Catalysis of isotopically labeled (18)O2/(12)C6H5(13)CH3 results in the formation of products containing (18)O, which indicates that both lattice and adsorbed oxygen are involved in the total oxidation of toluene. The role of adsorbed oxygen is activation of the C-H bond in toluene. The reaction network of the catalytic total oxidation of toluene consists of the following sequence: adsorption of toluene on the catalyst surface; activation of toluene by dehydrogenation with adsorbed oxygen; oxidation of activated toluene mainly by the lattice oxygen and re-oxidation of the reduced catalyst by dioxygen.