Microporosity and Catalytic Activity for Hydrodesulfurization of Pharmacosiderite Mo4P3O16 Synthesized at a Moderate Temperature.

Pharmacosiderite Mo4P3O16 (Pharma-MoPO) consists of [Mo4O4] cubane unit and [PO4] tetrahedral to form an open framework with a microporous structure similar to that of LTA-type zeolite. Although attractive applications are expected due to its microporous structure and redox-active components, its physicochemical properties have been poorly investigated due to the specificity of its synthesis, which requires a high hydrothermal synthesis temperature of 360 °C. In this study, we succeeded in synthesizing Pharma-MoPO by hydrothermal synthesis at 230 °C, which can be applied using a commercially available autoclave by changing the metal source. Through the study of the solids and liquids obtained after hydrothermal syntheses, the formation process of Pharma-MoPO under our studied synthesis conditions was proposed. Advanced characterizations provided detailed structural information on Pharma-MoPO, including the location site of a countercation NH4+. Pharma-MoPO could adsorb CO2 with the amount close to the number of cages without removing NH4+. Pharma-MoPO exhibited stable catalytic activity for the hydrodesulfurization of thiophene while maintaining its crystal structure, except for the introduction of sulfide by replacing lattice oxygens. Pharmacosiderite Mo4P3O16 was successfully obtained by hydrothermal synthesis at a moderate temperature, and its microporosity for CO2 adsorption and catalytic properties for hydrodesulfurization were discovered.

Feeble Single-Atom Pd Catalysts for H2 Production from Formic Acid.

Single-atom catalysts are thought to be the pinnacle of catalysis. However, for many reactions, their suitability has yet to be unequivocally proven. Here, we demonstrate why single Pd atoms (PdSA) are not catalytically ideal for generating H2 from formic acid as a H2 carrier. We loaded PdSA on three silica substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate functional groups. The Pd catalytic activity on amino-functionalized silica (SiO2-NH2/PdSA) was far higher than that of the thiol-based catalysts (SiO2-S-PdSA and SiO2-NHCS2-PdSA), while the single-atom stability of SiO2-NH2/PdSA against aggregation after the first catalytic cycle was the weakest. In this case, Pd aggregation boosted the reaction yield. Our experiments and calculations demonstrate that PdSA in SiO2-NH2/PdSA loosely binds with amine groups. This leads to a limited charge transfer from Pd to the amine groups and causes high aggregability and catalytic activity. According to the density functional calculations, the loose binding between Pd and N causes most of Pd's 4d electrons in amino-functionalized SiO2 to remain close to the Fermi level and labile for catalysis. However, PdSA chemically binds to the thiol group, resulting in strong hybridization between Pd and S, pulling Pd's 4d states deeper into the conduction band and away from the Fermi level. Consequently, fewer 4d electrons were available for catalysis.

In Situ Spectroscopic Study of CO2 Capture and Methanation over Ni-Ca Based Dual Functional Materials.

Carbon dioxide capture and reduction (CCR) to CH4 using dual-functional materials (DFMs) have recently attracted significant attention as a promising strategy for carbon capture and utilization. In this study, we investigate the mechanism of CCR to CH4 over Al2 O3 -supported Ni-Ca DFMs (Ni-Ca/Al2 O3 ) under cyclic feeds of model combustion exhaust (2.5 % CO2 +0 or 10 % O2 /N2 ) and H2 at 500 °C. Various spectroscopic analyses, including time-resolved in situ X-ray diffraction and X-ray absorption spectroscopy, were conducted during CO2 capture and the subsequent H2 -reduction steps. Based on these analyses, we propose a mechanism of CCR to CH4 over Ni-Ca based DFMs. During the CO2 capture step, the Ni0 species underwent complete oxidation in the presence of O2 to yield NiO. Subsequently, CO2 was captured through the interaction between the CaO surface and CO2 , resulting in the formation of CaCO3 layers on the CaO particles. When the gas flow was switched to H2 , NiO was partially to provide Ni0 sites, which acted as active sites for H2 -reduction of the adjacent CaCO3 layers to yield CaO and gas-phase products, CH4 and H2 O.

Continuous Unsteady-State De-NOx System via Tandem Water-Gas Shift, NH3 Synthesis, and NH3-SCR under Periodic Lean/Rich Conditions.

The development of urea-free and platinum group metal (PGM)-free catalytic systems for automotive emission control is a challenging task. Herein, we report a new de-NOx system using cyclic feeds of rich and lean gas mixtures with PGM-free catalysts. Initial catalyst screening tests showed that Cu/CeO2 with 5 wt % Cu loading was the most suitable for the water-gas shift reaction (WGS, CO + H2O → CO2 + H2), followed by the selective NH3 synthesis by the NO + H2 reaction. The unsteady-state system under alternating feeds of rich (0.1% NO + 0.5% CO + 1% H2O) and lean (0.1% NO + 2% O2 + 1% H2O) gas mixtures over a mixture of Cu/CeO2 and Cr-exchanged mordenite (CrMOR) showed higher NOx conversion than the steady-state (0.1% NO + 0.35% CO + 0.6% O2 + 1% H2O) reaction between 200 and 500 °C. The de-NOx mechanism under periodical rich/lean conditions was studied by operando infrared (IR) experiments. In the rich period, the WGS reaction on the Cu/CeO2 catalyst yield H2, which reduces NO to NH3 on the Cu/CeO2 catalyst. NH3 is then captured by the Brønsted acid sites of CrMOR. In the subsequent lean period, the adsorbed NH3 acts as a reductant for the selective catalytic reduction of NOx catalyzed by the Cr sites of CrMOR. This study demonstrates a new urea-free and PGM-free catalytic system that can provide an alternative de-NOx technology for automotive catalysis under periodic rich/lean conditions.

Mechanism of NH3-SCR over P/CeO2 Catalysts Investigated by Operando Spectroscopies.

This study reports a comprehensive investigation into the active sites and reaction mechanism for the selective catalytic reduction of NO by NH3 (NH3-SCR) over phosphate-loaded ceria (P/CeO2). Catalyst characterization and density functional theory calculations reveal that H3PO4 and H2P2O6 species are the dominant phosphate species on the P/CeO2 catalysts under the experimental conditions. The reduction/oxidation half-cycles (RHC/OHC) were investigated using in situ X-ray absorption near-edge structure for Ce L3-edge, ultraviolet-visible, and infrared (IR) spectroscopies together with online analysis of outlet products (operando spectroscopy). The Ce4+(OH-) species, possibly adjacent to the phosphate species, are reduced by NO + NH3 to produce N2, H2O, and Ce3+ species (RHC). The Ce3+ species is reoxidized by aqueous O2 (OHC). The results from IR spectroscopy suggest that the RHC initiates with the reaction between NO and Ce4+(OH-) to yield Ce3+ and gaseous HONO, which then react with NH3 to produce N2 and H2O via NH4NO2 intermediates.

Accelerated discovery of multi-elemental reverse water-gas shift catalysts using extrapolative machine learning approach.

Designing novel catalysts is key to solving many energy and environmental challenges. Despite the promise that data science approaches, including machine learning (ML), can accelerate the development of catalysts, truly novel catalysts have rarely been discovered through ML approaches because of one of its most common limitations and criticisms-the assumed inability to extrapolate and identify extraordinary materials. Herein, we demonstrate an extrapolative ML approach to develop new multi-elemental reverse water-gas shift catalysts. Using 45 catalysts as the initial data points and performing 44 cycles of the closed loop discovery system (ML prediction + experiment), we experimentally tested a total of 300 catalysts and identified more than 100 catalysts with superior activity compared to those of the previously reported high-performance catalysts. The composition of the optimal catalyst discovered was Pt(3)/Rb(1)-Ba(1)-Mo(0.6)-Nb(0.2)/TiO2. Notably, niobium (Nb) was not included in the original dataset, and the catalyst composition identified was not predictable even by human experts.

Prediction of Stable Surfaces of Metal Oxides through the Unsaturated Coordination Index.

This study proposes the unsaturated coordination index, σ, as a potential descriptor of the stability of metal-oxide surfaces cleaved from bulk. The value of σ, the number of missing bonds per unit area, can be obtained very quickly using only crystallographic data, namely, the bulk geometry. The surface energies of various binary oxides, with and without atom relaxation, were calculated. Their correlations with σ had good coefficients of determination (R2) values, particularly in high-symmetry crystals. The proposed descriptor is very useful for an initial evaluation of stable metal-oxide surfaces without conducting any surface model calculations.

Bifunctionality of Re Supported on TiO2 in Driving Methanol Formation in Low-Temperature CO2 Hydrogenation.

Low temperature and high pressure are thermodynamically more favorable conditions to achieve high conversion and high methanol selectivity in CO2 hydrogenation. However, low-temperature activity is generally very poor due to the sluggish kinetics, and thus, designing highly selective catalysts active below 200 °C is a great challenge in CO2-to-methanol conversion. Recently, Re/TiO2 has been reported as a promising catalyst. We show that Re/TiO2 is indeed more active in continuous and high-pressure (56 and 331 bar) operations at 125-200 °C compared to an industrial Cu/ZnO/Al2O3 catalyst, which suffers from the formation of methyl formate and its decomposition to carbon monoxide. At lower temperatures, precise understanding and control over the active surface intermediates are crucial to boosting conversion kinetics. This work aims at elucidating the nature of active sites and active species by means of in situ/operando X-ray absorption spectroscopy, Raman spectroscopy, ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Transient operando DRIFTS studies uncover the activation of CO2 to form active formate intermediates leading to methanol formation and also active rhenium carbonyl intermediates leading to methane over cationic Re single atoms characterized by rhenium tricarbonyl complexes. The transient techniques enable us to differentiate the active species from the spectator one on TiO2 support, such as less reactive formate originating from spillover and methoxy from methanol adsorption. The AP-XPS supports the fact that metallic Re species act as H2 activators, leading to H-spillover and importantly to hydrogenation of the active formate intermediate present over cationic Re species. The origin of the unique reactivity of Re/TiO2 was suggested as the coexistence of cationic highly dispersed Re including single atoms, driving the formation of monodentate formate, and metallic Re clusters in the vicinity, activating the hydrogenation of the formate to methanol.

Designing main-group catalysts for low-temperature methane combustion by ozone.

The catalytic combustion of methane at a low temperature is becoming increasingly key to controlling unburned CH4 emissions from natural gas vehicles and power plants, although the low activity of benchmark platinum-group-metal catalysts hinders its broad application. Based on automated reaction route mapping, we explore main-group elements catalysts containing Si and Al for low-temperature CH4 combustion with ozone. Computational screening of the active site predicts that strong Brønsted acid sites are promising for methane combustion. We experimentally demonstrate that catalysts containing strong Bronsted acid sites exhibit improved CH4 conversion at 250 °C, correlating with the theoretical predictions. The main-group catalyst (proton-type beta zeolite) delivered a reaction rate that is 442 times higher than that of a benchmark catalyst (5 wt% Pd-loaded Al2O3) at 190 °C and exhibits higher tolerance to steam and SO2. Our strategy demonstrates the rational design of earth-abundant catalysts based on automated reaction route mapping.

An automated reaction route mapping for the reaction of NO and active species on Ag4 clusters in zeolites.

A computational investigation of the catalytic reaction on multinuclear sites is very challenging. Here, using an automated reaction route mapping method, the single-component artificial force induced reaction (SC-AFIR) algorithm, the catalytic reaction of NO and OH/OOH species over the Ag42+ cluster in a zeolite is investigated. The results of the reaction route mapping for H2 + O2 reveal that OH and OOH species are formed over the Ag42+ cluster via an activation barrier lower than that of OH formation from H2O dissociation. Then, reaction route mapping is performed to examine the reactivity of the OH and OOH species with NO molecules over the Ag42+ cluster, resulting in the facile reaction path of HONO formation. With the aid of the automated reaction route mapping, the promotion effect of H2 addition on the SCR reaction was computationally proposed (boosting the formation of OH and OOH species). In addition, the present study emphasizes that automated reaction route mapping is a powerful tool to elucidate the complicated reaction pathway on multi-nuclear clusters.

In- and Ga-oxo clusters/hydrides in zeolites: speciation and catalysis for light-alkane activations/transformations.

Metal-exchanged zeolites have great potential to form unique active metal species and develop their catalysis by promoting small molecules such as light alkanes. Ga-exchanged zeolites have attracted attention as promising heterogeneous catalysts for dehydrogenative light-alkane transformations. The speciation of active Ga species in reduced and oxidized Ga-exchanged zeolites and their reaction mechanisms have been discussed in several studies based on experimental and theoretical investigations. In contrast, studies on In-exchanged zeolites have been far less explored, and thus active In-species have rarely been investigated. In this perspective, we summarized our investigations on In- and Ga-exchanged zeolites for light-alkane transformations. Our research group reported the formation of In-oxo clusters using the O2 treatment of In-CHA and their potential for the partial oxidation of CH4 (POM) at room temperature. We also observed the formation of In-hydrides in CHA zeolites during the preparation through reductive solid-state ion-exchange (RSSIE) and revealed their catalysis for non-oxidative C2H6 dehydrogenation (EDH). Their detailed structures and reaction mechanisms are discussed in combination with spectroscopic, kinetic, and theoretical studies. Furthermore, comparative studies on the formation of Ga-oxo clusters for POM at room temperature and the controlled formation of Ga-hydrides for selective EDH were conducted. The obtained results and insights are comprehensively discussed, including the relationship between the local structure of the active In/Ga species and reaction selectivity, as well as the influence of different zeolite frameworks on the formation of active species.

Continuous CO2 capture and methanation over Ni-Ca/Al2O3 dual functional materials.

Although Ni-Ca-based dual functional materials (DFMs) have been examined for CO2 capture and reduction with H2 (CCR) for the synthesis of CH4, their performance has generally been investigated using single reactors in an oxygen-free environment. In addition, continuous CCR operations have scarcely been investigated. In this study, continuous CCR for the production of CH4 was investigated using a double reactor system over Al2O3-supported Ni-Ca DFMs in the presence of O2. We found that a high Ca loading (Ni(10)-Ca(30)/Al2O3, 10 wt% Ni, and 30 wt% CaO) was necessary for reaction efficiency under isothermal conditions at 450 °C. The optimized DFM exhibited an excellent performance (46% CO2 conversion, 45% CH4 yield, and 97% CH4 selectivity, respectively) and good stability over 24 h. The structure and CCR activity of Ni(10)-Ca(30)/Al2O3 were studied using X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectrometry (EDS), temperature-programmed desorption (TPD), and temperature-programmed surface reaction (TPSR) techniques.

The reducibility and oxidation states of oxide-supported rhenium: experimental and theoretical investigations.

The activity and stability of supported metal catalysts, which exhibit high efficiency and activity, are significantly influenced by the interactions between the metal and the support, that is, metal-support interactions (MSIs). Here, we report an investigation of the MSIs between supported rhenium (Re) and oxide supports such as TiO2, SiO2, Al2O3, MgO, V2O5, and ZrO2 using experimental and computational approaches. The reducibility of the Re species was found to strongly depend on the oxide support. Experimental studies including temperature-programmed reduction by H2 as well as Re L3- and L1-edge X-ray absorption near edge structure (XANES) analysis revealed that the valency of the Re species started to decrease upon H2 reduction in the 200-400 °C range, except for Re on MgO, where the shift occurred at temperatures above 500 °C. The dependence of the Re L3- and L1-edge XANES spectra of the oxide-supported Re catalysts on the size of Re was also examined.

Dimethylacetamide-stabilized ruthenium nanoparticles for catalysing α-alkylations of amides with alcohols.

α-Alkylation reactions between amides and alcohols, with dimethylacetamide-stabilized Ru nanoparticles (NPs) as the catalyst, were investigated. The reactions proceeded with low catalyst loadings compared to metal complexes. Characterizations of the Ru NPs were performed by X-ray photoelectron spectroscopy, X-ray absorption fine structure spectroscopy, and various techniques. Control experiments revealed the reaction mechanisms, which proceeded via hydrogen autotransfer with alcohols.

Correction to "Trends in Surface Oxygen Formation Energy in Perovskite Oxides".

[This corrects the article DOI: 10.1021/acsomega.2c00702.].

Trends in Surface Oxygen Formation Energy in Perovskite Oxides.

Perovskite oxides comprise an important class of materials, and some of their applications depend on the surface reactivity characteristics. We calculated, using density functional theory, the surface O vacancy formation energy (E Ovac) for perovskite-structure oxides, with a transition metal (Ti-Fe) as the B-site cation, to estimate the catalytic reactivity of perovskite oxides. The E Ovac value correlated well with the band gap and bulk formation energy, which is a trend also found in other oxides. A low E Ovac value, which is expected to result in higher catalytic activity via the Mars-van Krevelen mechanism, was found in metallic perovskites such as CaCoO3, BaFeO3, and SrFeO3. On the other hand, titanates had high E Ovac values, typically exceeding 4 eV/atom, suggesting that these materials are less reactive when O vacancy formation is involved in the reaction mechanism.

N,N-Dimethylformamide-stabilized ruthenium nanoparticle catalyst for ß-alkylated dimer alcohol formation via Guerbet reaction of primary alcohols.

N,N-Dimethylformamide-stabilized Ru nanoparticles (NPs) provide a highly efficient catalyst for the Guerbet reaction of primary alcohols. DMF-modified Ru NPs were synthesized, and characterized by transition electron microscopy, and X-ray absorption spectroscopy, X-ray photoelectronspectroscopy, and Fourier-transform infrared spectroscopy. The Ru NP catalyst was highly durable during catalytic reactions under external additive/solvent-free conditions.

Super Mg2+ Conductivity around 10-3 S cm-1 Observed in a Porous Metal-Organic Framework.

We first report a solid-state crystalline "Mg2+ conductor" showing a superionic conductivity of around 10-3 S cm-1 at ambient temperature, which was obtained using the pores of a metal-organic framework (MOF), MIL-101, as ion-conducting pathways. The MOF, MIL-101⊃{Mg(TFSI)2}1.6 (TFSI- = bis(trifluoromethanesulfonyl)imide), containing Mg2+ inside its pores, showed a superionic conductivity of 1.9 × 10-3 S cm-1 at room temperature (RT) (25 °C) under the optimal guest vapor (MeCN), which is the highest value among all Mg2+-containing crystalline compounds. The Mg2+ conductivity in the MOF was estimated to be 0.8 × 10-3 S cm-1 at RT, by determining the transport number of Mg2+ (tMg2+ = 0.41), which is the level as high as practical use for secondary battery. Measurements of adsorption isotherms, pressure dependence of ionic conductivity, and in situ Fourier transform infrared measurements revealed that the "super Mg2+ conductivity" is caused by the efficient migration of the Mg2+ carrier with the help of adsorbed guest molecules.

Oxidation Catalysis over Solid-State Keggin-Type Phosphomolybdic Acid with Oxygen Defects.

Keggin-type phosphomolybdic acid (PMo12O40), treated with pyridine (Py), forms a crystalline material (PyPMo-HT) following heat treatment under an inert gas flow at ∼420 °C. Although this material is known to have attractive catalytic properties for gas-phase oxidation, the origin of this catalytic activity requires clarification. In this study, we investigated the crystal structure of PyPMo-HT. PyPMo-HT comprises a one-dimensional array of Keggin units and pyridinium cations (HPy), with an HPy/Keggin unit ratio of ∼1.0. Two oxygen atoms were removed from the Keggin unit during crystal structure transformation, which resulted in an electron being localized on the Mo atom in close contact with the adjacent Keggin unit. Upon the introduction of molecular oxygen, electron transfer from this Mo atom resulted in the formation of an electrophilic oxygen species that bridged two Keggin units. The electrophilic oxygen species acted as a catalytically active oxygen species, as confirmed by the selective oxidation of propylene. PyPMo-HT showed excellent catalytic activity for the selective oxidation of methacrolein, with the methacrylic acid yield being superior to that obtained with PMo12O40 and comparable to that obtained with an industrial Keggin-type polyoxometalate (POM) catalyst. The oxidation catalysis observed over PyPMo-HT provides a deeper understanding of POM-based industrial catalytic processes.