An Aqueous Redox Flow Battery Using CO2 as an Active Material with a Homogeneous Ir Catalyst.

For the application of CO2 as an energy storage material, a H2 storage system has been proposed based on the interconversion of CO2 and formic acid (or formate). However, energy losses are inevitable in the conversion of electrical energy to H2 as chemical energy (≈70 % electrical efficiency) and H2 to electrical energy (≈40 % electrical efficiency). To overcome these significant energy losses, we developed a system based on the interconversion of CO2 and formate for the direct storage and generation of electricity. In this paper, we report an aqueous redox flow battery system using homogeneous Ir catalysts with CO2 -formate redox pair. The system exhibited a maximum discharge capacity of 10.5 mAh (1.5 Ah L-1 ), capacity decay of 0.2 % per cycle, and total turnover number of 2550 after 50 cycles. During charging-discharging, in situ fluorescence X-ray absorption fine structure spectroscopy based on an online setup indicated that the active species was in a high valence state of IrIV .

Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid.

Recently, there has been a strong demand for technologies that use hydrogen as an energy carrier, instead of fossil fuels. Hence, new and effective hydrogen storage technologies are attracting increasing attention. Formic acid (FA) is considered an effective liquid chemical for hydrogen storage because it is easier to handle than solid or gaseous materials. This review presents recent advances in research into the development of homogeneous catalysts, primarily focusing on hydrogen generation by FA dehydrogenation. Notably, this review will aid in the development of useful catalysts, thereby accelerating the transition to a hydrogen-based society.

Ligand Design for Catalytic Dehydrogenation of Formic Acid to Produce High-pressure Hydrogen Gas under Base-free Conditions.

A series of Cp*Ir (Cp* = pentamethylcyclopentadienyl anion) complexes with amino-functionalized ligands were developed for the production of high-pressure H2 via catalytic dehydrogenation of formic acid (DFA) in water under base-free conditions. The Ir complexes with 2,2'-bipyridine (bpy) ligands bearing amino or alkylamino groups at the para positions exhibited high activity and stability for DFA compared with complexes containing bpy ligands bearing para-hydroxyl groups. In addition, para-amino groups afforded superior catalytic stability under high-pressure conditions compared with ortho-amino groups. By exploiting these amino-functionalized Cp*Ir complexes, it was possible to continuously produce high-pressure CO-free H2 via selective DFA in water upon the addition of concentrated FA (>99.5 wt %) to the base-free solution. Systematic investigation of the ligand effects on DFA revealed that the presence of alkylamino groups on the bpy ligand enhanced the catalytic activity (initial turnover frequency, TOF), although the stability decreased with increasing alkyl chain length on the amino groups. According to a Hammett plot, the increased catalytic activity of the Ir complexes after the introduction of amino-functionalized ligands may be attributable to the electron-donating effect of para-amino groups on the bpy ligand. Based on the experimental results, a reaction mechanism is proposed that involves a hydride intermediate whose stability is affected by the position of the amino groups on the bpy ligand, as confirmed through NMR studies.

Ligand Effect on the Stability of Water-Soluble Iridium Catalysts for High-Pressure Hydrogen Gas Production by Dehydrogenation of Formic Acid.

Aiming to develop a highly effective and durable catalyst for high-pressure H2 production from dehydrogenation of formic acid (DFA), the ligand effect on the catalytic activity and stability of Cp*Ir (Cp*:pentamethylcyclopentadienyl anion) complexes were investigated using 5 different kinds of N,N'-bidentate ligands (bipyridine, biimidazoline, pyridyl-imidazoline, pyridyl-pyrazole and picolinamide). The Ir complex with biimidazoline ligand exhibited the highest catalytic activity, but deactivation occurred readily at high pressure. The pyridine moiety in the ligand can enhance the stability of Ir complex catalysts for the high-pressure reaction. The Ir complex catalyst containing pyridyl-imidazoline ligand showed the high activity and best stability under the high-pressure conditions.

Kinetic Studies on Formic Acid Dehydrogenation Catalyzed by an Iridium Complex towards Insights into the Catalytic Mechanism of High-Pressure Hydrogen Gas Production.

Kinetic studies on the catalytic reaction mechanism of formic acid (FA) dehydrogenation were performed in the presence of a water-soluble iridium complex bearing a 4,4'-dihydroxy-2,2'-bipyridine ligand. Determination of kinetic isotope effects revealed that a shift of the rate-limiting step at low and high concentrations of FA can be caused by the pH dependence of the reaction steps. The proposed equation for the reaction rate corresponds well with the experimental results concerning the shift phenomena. Towards industrial application in future hydrogen fueling stations, this will able the design of a dehydrogenation system catalyzed by the iridium complex.

Effect of the ortho-Hydroxyl Groups on a Bipyridine Ligand of Iridium Complexes for the High-Pressure Gas Generation from the Catalytic Decomposition of Formic Acid.

The hydroxyl groups of a 2,2'-bipyridine (bpy) ligand near the metal center activated the catalytic performance of the Ir complex for the dehydrogenation of formic acid at high pressure. The position of the hydroxyl groups on the ligand affected the catalytic durability for the high-pressure H2 generation through the decomposition of formic acid. The Ir complex with a bipyridine ligand functionalized with para-hydroxyl groups shows a good durability with a constant catalytic activity during the reaction even under high-pressure conditions, whereas deactivation was observed for an Ir complex with a bipyridine ligand with ortho-hydroxyl groups (2). In the presence of high-pressure H2 , complex 2 decomposed into the ligand and an Ir trihydride complex through the isomerization of the bpy ligand. This work provides the development of a durable catalyst for the high-pressure H2 production from formic acid.

Development of Proton-Responsive Catalysts.

A changeable ligand, which involves in activation of a catalyst or assists a reaction, draws an increasing attention, in contrast to a classical ligand as spectator. Proton-responsive catalysts, which are capable of undergoing changes of properties on gaining/losing one or more protons, provides interesting features as follows: (i) catalyst activation by electronic effect, (ii) pH-tuning of water-solubility, and (iii) second-coordination-sphere interaction. On the basis of this catalyst design concept, we developed several highly efficient proton-responsive catalysts for CO2 hydrogenation as H2 storage, formic acid (FA) dehydrogenation as H2 production, and transfer hydrogenation. The transformable ligands of proton-responsive catalysts in promoting effective catalysis have aroused our interest. In this account, we summarize our efforts for the development and application of proton-responsive catalysts. Specifically, the important role of pH-dependent proton-responsive complexes will be discussed.

Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N'-Diimine Ligand.

We report a ruthenium complex containing an N,N'-diimine ligand for the selective decomposition of formic acid to H2 and CO2 in water in the absence of any organic additives. A turnover frequency of 12 000 h-1 and a turnover number of 350 000 at 90 °C were achieved in the HCOOH/HCOONa aqueous solution. Efficient production of high-pressure H2 and CO2 (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO. Mechanistic studies by NMR and DFT calculations indicate that there may be two competitive pathways for the key hydride transfer rate-determining step in the catalytic process.

Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature.

Carbon dioxide may constitute a source of chemicals and fuels if efficient and renewable processes are developed that directly utilize it as feedstock. Two of its reduction products are formic acid and methanol, which have also been proposed as liquid organic chemical carriers in sustainable hydrogen storage. Here we report that both the hydrogenation of carbon dioxide to formic acid and the disproportionation of formic acid into methanol can be realized at ambient temperature and in aqueous, acidic solution, with an iridium catalyst. The formic acid yield is maximized in water without additives, while acidification results in complete (98 %) and selective (96 %) formic acid disproportionation into methanol. These promising features in combination with the low reaction temperatures and the absence of organic solvents and additives are relevant for a sustainable hydrogen/methanol economy.

Iridium Catalyst Immobilized on Crosslinked Polyethyleneimine for Continuous Hydrogen Production Using Formic Acid.

Hydrogen is an alternative fuel that can play a critical role in achieving net zero emissions, leading to global environment sustainability. An iridium-immobilized catalyst based on polyethyleneimine (PEI) was synthesized and utilized for hydrogen production via formic acid dehydrogenation (FADH). Iridium complex is cross-linked with its ligand and PEI to form the immobilized catalyst, where the iridium content could be easily varied in the range of 1-10 %. The structure of the iridium-immobilized catalyst was confirmed using solid-state NMR, DNP NMR, and FTIR spectroscopies. The iridium-immobilized catalyst with PEI showed excellent catalytic activity for FADH, exhibiting the catalyst's highest turnover frequency (TOF) value of 73 200 h-1 and a large turnover number (TON) value of over 1 130 000. The catalyst could be used for continuous hydrogen production via FADH, exhibiting high durability for over 2 000 h with TON value of 332 889 without any degradation in catalytic activity. The obtained hydrogen gas was evaluated for power generation using a standard fuel cell, as well as achieved 5 h of stable power generation.

Enhancing continuous-flow reactions via compression-molding of solid catalysts and dilutants in packed-bed systems.

In this study, we present an improved packed-bed system designed for continuous-flow reactions using platinum (Pt)-black powder and silica gel (SiO2). The Pt-leaching from the reaction column is suppressed via compression-molding of the Pt and SiO2. Scanning electron microscopy results and particle-size distribution analysis demonstrate that crushed and downsized SiO2 is effective in suppressing outflow. Furthermore, we successfully conducted a scaled-up experiment of the flow reaction using a large column, achieving excellent productivity.

Iridium Catalyst Immobilized on Crosslinked Polyethyleneimine for Continuous Hydrogen Production Using Formic Acid.

Invited for this month's cover is provided by researchers from National Institute of Advanced Industrial Science and Technology (AIST) in Japan. The image shows the flow type continuous hydrogen production from formic acid and power generation by fuel cell achieved by the iridium catalyst immobilized on crosslinked polyethylene imine. The Research Article itself is available at 10.1002/cssc.202301282.

In situ formic acid dehydrogenation observation using a UV-vis-diffuse-reflectance spectroscopy system.

By applying a simple method on the generated gas concentration in the center of a round cell through high-speed stirring, we succeeded in continuously monitoring catalytic formic acid dehydrogenation using a newly developed in situ/operando UV-vis-diffuse-reflectance spectroscopy system, which can exhibit a high S/N ratio and reliable spectra without any mechanical errors from gas meters.

Rapid and continuous fabrication of TiO2 nanoparticles encapsulated by polyimide fine particles using a multistep flow-system and their application.

PI fine particles encapsulating a large number of TiO2 nanoparticles (PI FPs/TiO2 NPs) were successfully fabricated rapidly and continuously by the emulsion re-precipitation method using a multistep flow synthetic system. The fabricated material, PI FPs/TiO2 NPs, was spherical in structure with a diameter of 214 nm, and the mean size of TiO2 NPs was 5.2 nm. Line scan elemental analysis with SEM-EDX showed that the TiO2 NPs were disproportionately embedded near the surface of the PI FPs. UV-vis transmission spectra revealed high UV shielding efficiency of the PI FPs/TiO2 NPs as the NPs are located near the surface.

Development of a novel catalytic membrane reactor for heterogeneous catalysis in supercritical CO2.

A novel type of high-pressure membrane reactor has been developed for hydrogenation in supercritical carbon dioxide (scCO(2)). The main objectives of the design of the reactor are the separate feeding of hydrogen and substrate in scCO(2) for safe reactions in a continuous flow process, and to reduce the reaction time. By using this new reactor, hydrogenation of cinnamaldehyde into hydrocinnamaldehyde has been successfully carried out with 100% selectivity at 50 degrees C in 10 MPa (H(2): 1 MPa, CO(2): 9 MPa) with a flow rate of substrate ranging from 0.05 to 1.0 mL/min.

Highly efficient chemoselective N-acylation with water microreaction system in the absence of catalyst.

A high-speed, highly efficient chemoselective N-acylation by anhydride was achieved in the absence of catalyst for exothermic (DeltaH>0) and endothermic (DeltaH<0) acylation of various amines and anilines with the microreaction system of ambient water (micro-onH2O) and subcritical water (micro-subH2O), where the desired N-acylated products are chemoselectively obtained with high yield(s) and excellent selectivity (>95%).

An exceptionally rapid and selective hydrogenation of 2-cyclohexen-1-one in supercritical carbon dioxide.

Selective hydrogenation of 2-cyclohexen-1-one over Pt-MCM-41 proceeds at a very high rate and produces cyclohexanone with selectivity of 100% in a batch reactor; a marked increase in the reaction rate (TOF) from 2283 min(-1) to 5051 min(-1) is observed on increasing the pressure from 7 MPa to 14 MPa at 40 degrees C.

Amphiphilic block copolymer-stabilized gold nanoparticles for aerobic oxidation of alcohols in aqueous solution.

Stable Au nanoparticles in P123 aqueous solution using a simple method have been developed and the colloidal Au nanoparticles were successfully applied for the effective oxidation of various alcohols using molecular O2 as oxidant at 30 degrees C in aqueous solution.

Homogeneous photochemical oxidation via singlet O2 in supercritical CO2.

This communication describes the reaction chemistry of singlet oxygen in supercritical carbon dioxide, demonstrating rapid and quantitative conversion of alpha-terpinene to ascaridole.

Defining Pt-compressed CO2 synergy for selectivity control of furfural hydrogenation.

The development of a sustainable methodology for catalytic transformation of biomass-derived compounds to value-added chemicals is highly challenging. Most of the transitions are dominated by the use of additives, complicated reaction steps and large volumes of organic solvents. Compared to traditional organic solvents, alternative reaction media, which could be an ideal candidate for a viable extension of biomass-related reactions are rarely explored. Here, we elucidate a selective and efficient transformation of a biomass-derived aldehyde (furfural) to the corresponding alcohol, promoted in compressed CO2 using a Pt/Al2O3 catalyst. Furfural contains a furan ring with C[double bond, length as m-dash]C and an aldehyde group, and is extremely reactive in a hydrogen atmosphere, resulting in several by-products and a threat to alcohol selectivity as well as catalyst life. The process described has a very high reaction rate (6000 h-1) with an excellent selectivity/yield (99%) of alcohol, without any organic solvents or metal additives. This strategy has several key features over existing methodologies, such as reduced waste, and facile product separation and purification (reduced energy consumption). Combining the throughput of experimental observation and molecular dynamics simulation, indeed the high diffusivity of compressed CO2 controls the mobility of the compound, and eventually maintains the activity of the catalyst. Results are also compared for different solvents and solvent-less conditions. In particular, combination of an effective Pt catalyst with compressed CO2 provides an encouraging alternative solution for upgradation of biomass related platform molecules.