Integrated CO2 capture and reduction catalysis: Role of γ-Al2O3 support, unique state of potassium and synergy with copper.

Carbon dioxide capture and reduction (CCR) process emerges as an efficient catalytic strategy for CO2 capture and conversion to valuable chemicals. K-promoted Cu/Al2O3 catalysts exhibited promising CO2 capture efficiency and highly selective conversion to syngas (CO + H2). The dynamic nature of the Cu-K system at reaction conditions complicates the identification of the catalytically active phase and surface sites. The present work aims at more precise understanding of the roles of the potassium and copper and the contribution of the metal oxide support. While γ-Al2O3 guarantees high dispersion and destabilisation of the potassium phase, potassium and copper act synergistically to remove CO2 from diluted streams and promote fast regeneration of the active phase for CO2 capture releasing CO while passing H2. A temperature of 350℃ is found necessary to activate H2 dissociation and generate the active sites for CO2 capture. The effects of synthesis parameters on the CCR activity are also described by combination of ex-situ characterisation of the materials and catalytic testing.

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes.

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

CO2 Hydrogenation on Cu/Al2 O3 : Role of the Metal/Support Interface in Driving Activity and Selectivity of a Bifunctional Catalyst.

Selective hydrogenation of CO2 into methanol is a key sustainable technology, where Cu/Al2 O3 prepared by surface organometallic chemistry displays high activity towards CO2 hydrogenation compared to Cu/SiO2 , yielding CH3 OH, dimethyl ether (DME), and CO. CH3 OH formation rate increases due to the metal-oxide interface and involves formate intermediates according to advanced spectroscopy and DFT calculations. Al2 O3 promotes the subsequent conversion of CH3 OH to DME, showing bifunctional catalysis, but also increases the rate of CO formation. The latter takes place 1) directly by activation of CO2 at the metal-oxide interface, and 2) indirectly by the conversion of formate surface species and CH3 OH to methyl formate, which is further decomposed into CH3 OH and CO. This study shows how Al2 O3 , a Lewis acidic and non-reducible support, can promote CO2 hydrogenation by enabling multiple competitive reaction pathways on the oxide and metal-oxide interface.

Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol.

Methyl formate synthesis by hydrogenation of carbon dioxide in the presence of methanol offers a promising path to valorize carbon dioxide. In this work, silica-supported silver nanoparticles are shown to be a significantly more active catalyst for the continuous methyl formate synthesis than the known gold and copper counterparts, and the origin of the unique reactivity of Ag is clarified. Transient in situ and operando vibrational spectroscopy and DFT calculations shed light on the reactive intermediates and reaction mechanisms: a key feature is the rapid formation of surface chemical species in equilibrium with adsorbed carbon dioxide. Such species is assigned to carbonic acid interacting with water/hydroxyls on silica and promoting the esterification of formic acid with adsorbed methanol at the perimeter sites of Ag on SiO2 to yield methyl formate. This study highlights the importance of employing combined methodologies to verify the location and nature of active sites and to uncover fundamental catalytic reaction steps taking place at metal-support interfaces.

Synergistic interplay of Zn and Rh-Cr promoters on Ga2O3 based photocatalysts for water splitting.

The photocatalytic water splitting activity of a wide-bandgap material, Ga2O3, is greatly boosted with the addition of a Zn and Rh-Cr co-catalyst at optimum loadings. To date, however, the exact roles of the co-catalysts and particularly the origin of their synergistic functions have not been clarified. Herein, we present how the optimum Zn loading on Ga2O3 leads to creation of a ZnGa2O4/Ga2O3 heterojunction favorable for charge separation through information on the occupied and unoccupied electronic states of Zn and Ga elucidated by X-ray absorption and emission spectroscopic methods. The function of Rh-Cr as an electron sink and reduction site was proven by photocatalytic experiments using an electron scavenger (Ag+) and by learning where Ag deposits and its effects on photocatalytic activity. Finally, perturbation of the Zn electronic structure by photoactivation was evidenced by modulation excitation X-ray absorption spectroscopy. Importantly, Rh-Cr markedly enhanced the level of the perturbation, serving as proof of the direct communication and synergy between the electronic states of Zn, present in ZnGa2O4, and Rh-Cr deposited on Ga2O3.

CO2 Activation over Catalytic Surfaces.

This article describes the main strategies to activate and convert carbon dioxide (CO2 ) into valuable chemicals over catalytic surfaces. Coherent elements such as common intermediates are identified in the different strategies and concisely discussed based on the reactivity of CO2 with the aim to understand the decisive factors for selective and efficient CO2 conversion.

CO2 -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface.

Methanol synthesis by CO2 hydrogenation is a key process in a methanol-based economy. This reaction is catalyzed by supported copper nanoparticles and displays strong support or promoter effects. Zirconia is known to enhance both the methanol production rate and the selectivity. Nevertheless, the origin of this observation and the reaction mechanisms associated with the conversion of CO2 to methanol still remain unknown. A mechanistic study of the hydrogenation of CO2 on Cu/ZrO2 is presented. Using kinetics, in situ IR and NMR spectroscopies, and isotopic labeling strategies, surface intermediates evolved during CO2 hydrogenation were observed at different pressures. Combined with DFT calculations, it is shown that a formate species is the reaction intermediate and that the zirconia/copper interface is crucial for the conversion of this intermediate to methanol.

Air-stable gold nanoparticles ligated by secondary phosphine oxides for the chemoselective hydrogenation of aldehydes: crucial role of the ligand.

The synthesis of air-stable and homogeneous gold nanoparticles (AuNPs) employing tert-butyl(naphthalen-1-yl)phosphine oxide as supporting ligand is described via NaBH4 reduction of a Au(I) precursor, [(tert-butyl(naphthalen-1-yl)phosphine oxide)AuCl]2. This highly reproducible and simple procedure furnishes small (1.24 ± 0.16 nm), highly soluble nanoparticles that are found to be highly active catalysts for the hydrogenation of substituted aldehydes, giving high conversions and chemoselectivities for a wide variety of substrates. In addition to catalytic studies the role of the novel stabilizer in the remarkable activity and selectivity exhibited by this system was interrogated thoroughly using a wide range of techniques, including ATR FT-IR, HRMAS NMR, XPS, and EDX spectroscopy. In particular, isotopic labeling experiments enabled us to probe the coordination mode adopted by the SPO ligand bound to the nanoparticle surface by ATR FT-IR spectroscopy. In combination with a series of control experiments we speculate that the SPO ligand demonstrates ligand-metal cooperative effects and plays a seminal role in the heterolytic hydrogenation mechanism.

An atomistic picture of the regeneration process in dye sensitized solar cells.

A highly efficient mechanism for the regeneration of the cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II) sensitizing dye (N3) by I(-) in acetonitrile has been identified by using molecular dynamics simulation based on density functional theory. Barrier-free complex formation of the oxidized dye with both I(-) and , and facile dissociation of and from the reduced dye are key steps in this process. In situ vibrational spectroscopy confirms the reversible binding of I(2) to the thiocyanate group. Additionally, simulations of the electrolyte near the interface suggest that acetonitrile is able to cover the (101) surface of anatase with a passivating layer that inhibits direct contact of the redox mediator with the oxide, and that the solvent structure specifically enhances the concentration of I(-) at a distance which further favors rapid dye regeneration.

Towards Higher NH3 Faradaic Efficiency: Selective-Poisoning of HER Active Sites by Co-Feeding CO in NO Electroreduction.

Direct electroreduction of nitric oxide offers a promising avenue to produce valuable chemicals, such as ammonia, which is an essential chemical to produce fertilizers. Direct ammonia synthesis from NO in a polymer electrolyte membrane (PEM) electrolyzer is advantageous for its continuous operation and excellent mass transport characteristics. However, at a high current density, the faradaic efficiency of NO electroreduction reaction is limited by the competing hydrogen evolution reaction (HER). Herein, we report a CO-mediated selective poisoning strategy to enhance the faradaic efficiency (FE) towards ammonia by suppressing the HER. In the presence of only NO at the cathode, Pt/C and Pd/C catalysts showed a lower FE towards NH3 than to H2 due to the dominating HER. Cu/C catalyst showed a 78 % FE towards NH3 at 2.0 V due to the stronger binding affinity to NO* compared to H*. By co-feeding CO, the FE of Cu/C catalyst towards NH3 was improved by 12 %. More strikingly, for Pd/C, the FE towards NH3 was enhanced by 95 % with CO co-feeding, by effectively suppressing HER. This is attributed to the change of the favorable surface coverage resulting from the selective and competitive binding of CO* to H* binding sites, thereby improving NH3 selectivity.

Dimethyl carbonate synthesis from CO2 and methanol over CeO2: elucidating the surface intermediates and oxygen vacancy-assisted reaction mechanism.

Surface intermediate species and oxygen vacancy-assisted mechanism over CeO2 catalyst in the direct dimethyl carbonate (DMC) synthesis from carbon dioxide and methanol are suggested by means of transient spectroscopic methodologies in conjunction with multivariate spectral analysis. How the two reactants, i.e. CO2 and methanol, interact with the CeO2 surface and how they form decisive surface intermediates leading to DMC are unraveled by DFT-based molecular dynamics simulation by precise statistical sampling of various configurations of surface states and intermediates. The atomistic simulations and uncovered stability of different intermediate states perfectly explain the unique DMC formation profile experimentally observed upon transient operations, strongly supporting the proposed oxygen vacancy-assisted reaction mechanism.

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.

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu-Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol.

The direct synthesis of methanol via the hydrogenation of CO2, if performed efficiently and selectively, is potentially a powerful technology for CO2 mitigation. Here, we develop an active and selective Cu-Zn/SiO2 catalyst for the hydrogenation of CO2 by introducing copper and zinc onto dehydroxylated silica via surface organometallic chemistry and atomic layer deposition, respectively. At 230 °C and 25 bar, the optimized catalyst shows an intrinsic methanol formation rate of 4.3 g h-1 gCu-1 and selectivity to methanol of 83%, with a space-time yield of 0.073 g h-1 gcat-1 at a contact time of 0.06 s g mL-1. X-ray absorption spectroscopy at the Cu and Zn K-edges and X-ray photoelectron spectroscopy studies reveal that the CuZn alloy displays reactive metal support interactions; that is, it is stable under H2 atmosphere and unstable under conditions of CO2 hydrogenation, indicating that the dealloyed structure contains the sites promoting methanol synthesis. While solid-state nuclear magnetic resonance studies identify methoxy species as the main stable surface adsorbate, transient operando diffuse reflectance infrared Fourier transform spectroscopy indicates that µ-HCOO*(ZnOx) species that form on the Cu-Zn/SiO2 catalyst are hydrogenated to methanol faster than the µ-HCOO*(Cu) species that are found in the Zn-free Cu/SiO2 catalyst, supporting the role of Zn in providing a higher activity in the Cu-Zn system.

Electrified Conversion of Contaminated Water to Value: Selective Conversion of Aqueous Nitrate to Ammonia in a Polymer Electrolyte Membrane Cell.

The application of a polymer electrolyte membrane (PEM) electrolytic cell for continuous conversion of nitrate, one of the contaminants in water, to ammonia at the cathode was explored in the present work. Among carbon-supported metal (Cu, Ru, Rh and Pd) electrocatalysts, the Ru-based catalyst showed the best performance. By suppressing the competing hydrogen evolution reaction at the cathode, it was possible to reach 94 % faradaic efficiency for nitrate reduction towards ammonium. It was important to match the rate of the anodic reaction with the cathodic reaction to achieve high faradaic efficiency. By recirculating the effluent stream, 93 % nitrate conversion was achieved in 8 h of constant current electrolysis at 10 mA cm-2 current density. The presented approach offers a promising path towards precious NH3 production from nitrate-containing water that needs purification or can be obtained after capture of gaseous NOx pollutants into water, leading to waste-to-value conversion.

Correction to "Silica-Supported PdGa Nanoparticles: Metal Synergy for Highly Active and Selective CO2-to-CH3OH Hydrogenation".

[This corrects the article DOI: 10.1021/jacsau.1c00021.].

Evaluation of CO2 and H2O Adsorption on a Porous Polymer Using DFT and In Situ DRIFT Spectroscopy.

Numerous hyper-cross-linked polymers (HCPs) have been developed as CO2 adsorbents and photocatalysts. Yet, little is known of the CO2 and H2O adsorption mechanisms on amorphous porous polymers. Gaining a better understanding of these mechanisms and determining the adsorption sites are key to the rational design of improved adsorbents and photocatalysts. Herein, we present a unique approach that combines density functional theory (DFT), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and multivariate spectral analysis to investigate CO2 and H2O adsorption sites on a triazine-biphenyl HCP. We found that CO2 and H2O adsorb on the same HCP sites albeit with different adsorption strengths. The primary amines of the triazines were identified as favoring strong CO2 binding interactions. Given the potential use of HCPs for CO2 photoreduction, we also investigated CO2 and H2O adsorption under transient light irradiation. Under irradiation, we observed partial CO2 and H2O desorption and a redistribution of interactions between the H2O and CO2 molecules that remain adsorbed at HCP adsorption sites.

Diastereodivergent asymmetric sulfa-Michael additions of α-branched enones using a single chiral organic catalyst.

A significant limitation of modern asymmetric catalysis is that, when applied to processes that generate chiral molecules with multiple stereogenic centers in a single step, researchers cannot selectively access the full matrix of all possible stereoisomeric products. Mirror image products can be discretely provided by the enantiomeric pair of a chiral catalyst. But modulating the enforced sense of diastereoselectivity using a single catalyst is a largely unmet challenge. We document here the possibility of switching the catalytic functions of a chiral organic small molecule (a quinuclidine derivative with a pendant primary amine) by applying an external chemical stimulus, in order to induce diastereodivergent pathways. The strategy can fully control the stereochemistry of the asymmetric conjugate addition of alkyl thiols to α-substituted α,ß-unsaturated ketones, a class of carbonyls that has never before succumbed to a catalytic approach. The judicious choice of acidic additives and reaction media switches the sense of the catalyst's diastereoselection, thereby affording either the syn or anti product with high enantioselectivity.

Greener and facile synthesis of Cu/ZnO catalysts for CO2 hydrogenation to methanol by urea hydrolysis of acetates.

Cu/ZnO-based catalysts for methanol synthesis by CO x hydrogenation are widely prepared via co-precipitation of sodium carbonates and nitrate salts, which eventually produces a large amount of wastewater from the washing step to remove sodium (Na+) and/or nitrate (NO3 -) residues. The step is inevitable since the remaining Na+ acts as a catalyst poison whereas leftover NO3 - induces metal agglomeration during the calcination. In this study, sodium- and nitrate-free hydroxy-carbonate precursors were prepared via urea hydrolysis co-precipitation of acetate salt and compared with the case using nitrate salts. The Cu/ZnO catalysts derived from calcination of the washed and unwashed precursors show catalytic performance comparable to the commercial Cu/ZnO/Al2O3 catalyst in CO2 hydrogenation at 240-280 °C and 331 bar. By the combination of urea hydrolysis and the nitrate-free precipitants, the catalyst preparation is simpler with fewer steps, even without the need for a washing step and pH control, rendering the synthesis more sustainable.

PEM Electrolysis-Assisted Catalysis Combined with Photocatalytic Oxidation towards Complete Abatement of Nitrogen-Containing Contaminants in Water.

Electrolysis-assisted nitrate (NO3 - ) reduction is a promising approach for its conversion to harmless N2 from waste, ground, and drinking water due to the possible process simplicity by in-situ generation of H2 /H/H+ by water electrolysis and to the flexibility given by tunable redox potential of electrodes. This work explores the use of a polymer electrolyte membrane (PEM) electrochemical cell for electrolysis-assisted nitrate reduction using SnO2 -supported metals as the active cathode catalysts. Effects of operation modes and catalyst materials on nitrate conversion and product selectivity were studied. The major challenge of product selectivity, namely complete suppression of nitrite (NO2 - ) and ammonium (NH4 + ) ion formation, was tackled by combining with simultaneous photocatalytic oxidation to drive the overall reaction towards N2 formation.

Silica-Supported PdGa Nanoparticles: Metal Synergy for Highly Active and Selective CO2-to-CH3OH Hydrogenation.

The direct conversion of CO2 to CH3OH represents an appealing strategy for the mitigation of anthropogenic CO2 emissions. Here, we report that small, narrowly distributed alloyed PdGa nanoparticles, prepared via surface organometallic chemistry from silica-supported GaIII isolated sites, selectively catalyze the hydrogenation of CO2 to CH3OH. At 230 °C and 25 bar, high activity (22.3 molMeOH molPd -1 h-1) and selectivity for CH3OH/DME (81%) are observed, while the corresponding silica-supported Pd nanoparticles show low activity and selectivity. X-ray absorption spectroscopy (XAS), IR, NMR, and scanning transmission electron microscopy-energy-dispersive X-ray provide evidence for alloying in the as-synthesized material. In situ XAS reveals that there is a dynamic dealloying/realloying process, through Ga redox, while operando diffuse reflectance infrared Fourier transform spectroscopy demonstrates that, while both methoxy and formate species are observed in reaction conditions, the relative concentrations are inversely proportional, as the chemical potential of the gas phase is modulated. High CH3OH selectivities, across a broad range of conversions, are observed, showing that CO formation is suppressed for this catalyst, in contrast to reported Pd catalysts.