High-temperature Reactor Research Articles

Hydrogen Yield Enhancement in Biogas Dry Reforming with a Ni/Cr Catalyst: A Numerical Study

This numerical study investigates the impact of the reaction temperature, molar ratio of CH4:CO2, and catalyst porosity (εp) on the H2 yield and H2 selectivity during biogas dry reforming over a Ni/Cr catalyst. Using COMSOL Multiphysics, we conducted detailed simulations to elucidate the underlying reaction characteristics. Our findings reveal that increasing εp from 0.1 to 0.95 significantly provides a 5 times increase in H2 production and a 2.3% increase in H2 selectivity while simultaneously reducing CO selectivity by 2.3%. This effect is attributed to the improved mass transfer within the catalyst bed, leading to more efficient reactant conversion and product formation. Additionally, we observed a strong correlation between higher reaction temperatures and increased H2 yield and H2 selectivity. By optimizing these operational parameters, our results suggest that Ni/Cr catalysts can be effectively employed for the sustainable production of H2 from biogas.

Epitaxial Growth of Multicolor Lanthanide MOFs by Ultrasound for Photonic Barcodes.

Epitaxially grown lanthanide metal-organic frameworks (Ln MOFs) exhibit multicolor and characteristic Ln emission with sharp emission bands, which are of great value in the field of information security and anti-counterfeiting. Epitaxial growth of Ln MOFs is generally achieved by solvothermal or hydrothermal methods, which suffer from challenges such as high reaction temperature and long growth time. Here, we report the fast epitaxial growth of multicolor lanthanide MOFs by an ultrasonic method at room temperature. The TbSmSQ shows a core-shell type structure with the Tb ion in the core and Sm in the shell within one crystal and exhibits the characteristic emission lines of Tb and Sm, respectively. The nonporous structure and large distance between lanthanide ions effectively avoid the influence of solvent vapor on the intensity and color of luminescence emission. Its application as photonic barcodes has been studied. This work demonstrates the feasibility of epitaxial growth of multicolor Ln MOFs by the ultrasonic method and its value for anti-counterfeiting and information security applications.

Mineralization reaction between CO2 and coal ash produced from underground coal gasification: Implication for in situ carbon sequestration

Underground coal gasification (UCG) represents a promising clean and low-carbon energy technology, which could create a suitable cavity for in situ carbon sequestration by mineralization reaction between CO2 and coal ash produced from UCG. This may assist in achieving a net-zero carbon emission goal for UCG projects. To determine the carbonation efficiency and mineralization potential of CO2 mineral sequestration in abandoned UCG cavity, coal ash produced from the gasification of three different low-rank coal samples was used in this study. A comparative experiment was conducted using a group of high-calcium fly ash from a coal-fired power plant. All mineralization reaction experiments were performed in a high-temperature and high-pressure reactor, with CO2 pressures ranging from 2 to 8 MPa and temperatures ranging from 40 to 80°C. These conditions were selected to simulate the sequestration conditions in the UCG cavity. Real-time monitoring of CO2 pressure in the reactor was used to assess the impact of solid-to-water ratio, temperature, and pressure on the CO2 mineralization. X-ray diffraction and scanning electron microscopy were employed to identify the presence of newly formed carbonate minerals associated with mineralization reaction. The results indicated that the coal ash produced by gasification pretreatment at 900°C contains a substantial quantity of alkaline-earth oxides, such as calcium oxide (CaO), with a relative mass fraction reaching 25.9%. It provided an adequate supply of alkali metal ions for the mineralization reaction, which exhibited comparable efficacy in mineralizing CO2 to that observed in high-calcium fly ash. Without stirring, at lower solid-to-water ratio, the maximum amount of CO2 consumed through mineralization was increased by up to 74.12%. Carbonation efficiency decreased with rising temperatures below 70°C due to the limited dissolution of CO2 in water, it increased with elevated pressure but decreased in the supercritical state, potentially attributable to the dissolution of carbonate minerals in a supercritical CO2 environment. The process of mineralization reaction between CO2 and coal ash aligned well with the Surface Coverage Model (R2 values ranging from 0.92 to 0.99). A preliminary estimation based on Chinese coal reserves revealed that the potential of CO2 sequestration capacity in UCG cavities by mineralization ranging from 29 to 102 Gt, an additional 517 Gt CO2 may be stored when filled with fly ash. This paper provides theoretical bases for predicting the maximum carbonation efficiency under high-pressure and high-temperature conditions in UCG cavities, and research directions for achieving a net-zero carbon emission goal for UCG projects.

Synthesis of Few Layers Graphene Sheets from Graphite Rod via Electrochemical Exfoliation

Graphene has many excellent properties in mechanical strength, electrical conductivity, optical transparency and thermal conductivity. The basic unit of graphene is made of hexagonal ring of carbon shape. The production of graphene in large amounts can be done using conventional ways such as chemical vapour deposition (CVD). However, the cost production is very high due to high reaction temperature. Therefore, electrochemical exfoliation could become a promising method in future because of its simple, low cost and large-scale production. Electrochemical method is performed in the manner by connecting the graphite rod to the positive terminal (anode) while the copper sheet is connected to the negative terminal (cathode) and both of were immersed into electrolyte with a distance between them. Then, due to the potential difference, the exfoliation of graphite into graphene sheets occurs. X-Ray Diffraction revealed that high amount of exfoliated graphene sheets was synthesized successfully where the peak was seen at approximately 26.60°. Fourier Transform Infrared confirmed the synthesized of graphene oxide (GO) sheets (by using H2SO4 as electrolyte) shows the higher intensity of O-H band because of strongest oxidation behaviour of H2SO4 acid among all electrolytes used in experiment. Besides. SEM images show that the morphologies of the exfoliated graphene sheets have stacked, flaky-like, wrinkled and crumpled structures.

Introduction of Molecular Complexity via the Cross-Coupling of Lithium 1,4-Dioxene with Aryl Bromides.

The synthetic potential of substituted 1,4-dioxenes is well recognised, although the chemistry of 2-aryl-1,4-dioxenes is relatively unexplored. Their transition metal-catalysed synthesis has been limited to Stille-type cross-coupling chemistry, typically showing long reaction times, or proceeding at high reaction temperatures. Here we present a facile and general methodology for the cross-coupling of aryl bromides with lithium 1,4-dioxene, affording a range of 2-aryl-1,4-dioxenes in generally good yields. We highlight the synthetic applicability of this transformation at multigram scale, and demonstrate the versatility of the products by conversion of the dioxene units to various carbonyl-based functionalities. Additionally, we present a concise two-step synthesis of an arylated analogue to a known 1,4-dioxene-based antifungal agent.

Poly(butylene succinate) Microparticles Prepared Through Green Suspension Polycondensations

AbstractThe demand for sustainable polymer particles production is growing, driven by the need for efficient, biocompatible, and biodegradable materials. In this context, the present study explores the production of poly(butylene succinate) (PBS) particles in a single step using a green heterogeneous suspension process, using vegetable oil as the suspending medium. Particularly, the effects of oil type (soybean, corn, sunflower), dispersed phase holdup (10–30 wt.%), stabilizers (Span 20, Span 80, Tween 80, Brij 52, Brij 93, Igepal‐co‐520, Polyglycerol polyricinoleate (PGPR)), reaction time (1–5 h), and temperature (100–160 °C) on the suspension polymerization are investigated. Results indicate that particle size and shape are influenced by the vegetable oil and stabilizer. Additionally, it is shown that the particle size distribution is affected by the use of a sonicator, allowing the manufacture of even smaller microsized particles. Based on the results, a 30 wt.% holdup in corn oil with a blend of surfactants can be recommended, producing spherical particles with an average diameter of 100 µm. Moreover, higher reaction temperatures (160 °C) and longer reaction times (5 h) positively impacted the molar mass of the obtained particles. Finally, cytotoxicity tests using Bone Marrow‐Derived Macrophages cells confirmed the safe use of PBS microparticles at concentrations up to 1000 µg mL⁻¹

Development of Whole System Digital Twins for Advanced Reactors: Leveraging Graph Neural Networks and SAM Simulations

In this work, we introduce a novel method to develop whole system digital twins (DTs) for advanced nuclear reactors. This method treats a complex reactor system as a heterogeneous graph: with the system components as different types of graph nodes and their physical interconnections as edges. Based on the heterogeneous graph, a graph neural network combining graph convolution and temporal node attention is developed as the DT, facilitating a comprehensive understanding of the system’s dynamic behavior. By utilizing the System Analysis Module (SAM) code for simulating various operational transients, we develop a graph-based database that trains the DT. This DT is characterized by two primary functions: It can infer the entire system’s status using sparse node information, and it can predict the progress of transients based on current and historical system information. Our approach is validated through case studies on the Experimental Breeder Reactor II (EBR-II) system and a generic Fluoride-salt-cooled High-temperature Reactor (gFHR), demonstrating the DT’s accuracy in forecasting operational transients. The DT’s rapid computation capabilities enhance its potential for supporting advanced reactor operations, offering benefits in intelligent simulation, autonomous control, and anomaly detection, paving the way for improved safety analysis and intelligent component health management for advanced reactor systems and reducing their operations and maintenance cost.

Experimental quantification of interparticle forces in gas-solid fluidized beds operating at temperatures from ambient to 1500 °C

The successful design and operation of high-temperature gas-solid fluidized bed reactors require a deep understanding of interparticle forces (IPFs). However, experimentally quantifying IPFs at elevated temperatures has been a significant challenge due to the lack of suitable methods. This study addresses this gap by introducing a simple yet reliable experimental approach to quantify IPFs in a gas-solid fluidized bed across a temperature range from ambient to 1500 °C. The experimental results reveal that IPFs increase gradually with temperatures up to 1200 °C and become more pronounced at higher temperatures. Smaller particles, or those prone to changes in morphological, structural, and chemical properties—such as softening, sintering, or the formation of low-melting-point eutectic compounds at high temperatures—intensify IPFs significantly. This phenomenon is corroborated by our experiments and comparison with literature data across various temperatures and particle types. Finally, two empirical correlations are proposed to predict IPFs as temperature and particle diameter functions for coarse particles in high-temperature fluidized beds. These findings enhance the understanding of IPFs in high-temperature fluidized beds and are valuable for developing such systems for industrial applications.

Thermal hydraulic analysis of a high-temperature gas reactor steam generator after loss of feed water accidents

The helical coil steam generator is widely employed in the energy conversion process of high-temperature gas-cooled reactors for its high thermal efficiency in producing superheated steam within the helical tubes. These tubes necessitate materials specifically designed to endure high temperatures, prevent ruptures, and ensure durability under various operational conditions. This study aims to identify the maximum temperatures arising from potential transients in the secondary system and to propose immediate safety measures for minimizing associated risks. The RELAP5/MOD3.4 code was used to simulate the behavior of the next generation nuclear plant steam generator's conceptual design using steady-state conditions. Following the validation of the model, the established steady-state conditions were utilized to simulate accident scenarios, including the feed water line break and the loss of feed water flow to the steam generator. The transient scenarios assumptions include closed flap valves and retained hot helium in the shell side. The simulation tasks were conducted both with and without activating the depressurization system, in order to assess its effect on the temperature of tubes on the wall side. The analysis results indicate that tube wall temperatures can reach 720 °C at the steam generator outlet region and 620 °C at the weld region. The immediate activation of the depressurization system with a controlled relief valve can effectively reduce these temperatures by 239 °C in the steam generator outlet and by 133 °C in the weld region. This also lowers the steam generator's secondary side pressure. As a result, an upgrade and enhancement of operational procedures is straightforward.

Photoelectrocatalytic [4+2] Annulation for S-Heterocycle Assembly Enabled by Proton-Coupled Electron Transfer (PCET).

Cross-dehydrogenative couplings (CDC) present an efficient strategy for the assembly of biorelevant heterocycles, but are thus far largely limited to toxic transition metals and rather harsh reaction conditions. In sharp contrast, we, herein report on a mild photoelectrocatalyzed CDC-[4+2] annulation enabling the synthesis of functionalized isothiochromenes enabled by a proton-coupled electron transfer (PCET) strategy. The transformative photoelectrocatalysis obviated toxic transition-metal, high reaction temperatures, and stoichiometric chemical redox reagents. This approach was characterized by exceedingly mild conditions, ample substrate scope, and a commercially available catalyst. Gram-scale reactions and a telescoped synthesis route reflected the unique potential in the green synthesis of important S-heterocycles.

Mild Catalyst- and Additive-Free Three-Component Synthesis of 3-Thioisoindolinones and Tricyclic γ-Lactams Accelerated by Microdroplet Chemistry.

Isoindolinones, bearing both γ-lactam and aromatic rings, draw extensive interest in organic, pharmaceutical, and medicinal communities as they are important structural motifs in many natural products, bioactive compounds, and pharmaceuticals. As the main contributor to isoindolinone synthesis, metal catalysis is associated with many drawbacks including essential use of toxic/precious metals and excessive additives, high reaction temperatures, specially predesigned starting materials, and long reaction times (typically 8-30 h). In this study, we developed a catalyst- and additive-free, minute-scale, and high-yield microdroplet method for tricomponent isoindolinone synthesis at mild temperatures. By taking advantage of the astonishing reaction acceleration (1.9 × 102-9.4 × 103 acceleration factor range with a typical rate acceleration factor of 1.51 × 103 for the prototype reaction as the ratio of rate constants by microdroplet and bulk phase), 12 3-thioisoindolinones and two tricyclic γ-lactams were synthesized using various 2-acylbenzaldehydes, amines, and thiols with satisfactory yields ranging from 85% to 97% as well as a scale-up rate of 3.49 g h-1. Because of the advantages (no use of any catalysts or additives, mild temperature, rapid and satisfactory conversion, broad substrate scope, and gram scalability), the microdroplet method represents an attractive alternative to metal catalysis for laboratory synthesis of isoindolinones and their derivatives.

Efficient biodegradation of poly(butylene adipate-co-terephthalate) in mild temperature by cutinases derived from a marine fungus

Poly(butylene adipate-co-terephthalate) (PBAT) waste gradually accumulates in the environment, posing ecological risks. Enzymatic hydrolysis holds great potential in the end-of-life management of PBAT, but reported enzymes require high reaction temperatures, limiting their practical industrial applications. In this study, we discovered that the marine fungus Alternaria alternata FB1 can efficiently degrade PBAT at 28 °C. Two cutinases designated as AaCut4 and AaCut10, were identified and verified as key enzymes responsible for this degradation process. Notably, the recombinant AaCut10 was able to depolymerize 82.14 % PBAT within 24 h and fully decompose it within 48 h at 37 °C. Through protein engineering, the yield of terephthalic acid monomer was increased to 96.01 %, highlighting its potential for facilitating PBAT upcycling. Furthermore, based on the investigation of the distribution patterns of PBAT hydrolases, novel degradative agents have been identified within unique ecological niches, leading to the establishment of a comprehensive screening repository of PBAT hydrolases. Overall, our study provides new candidates for enzymatic PBAT recycling with low energy consumption and offers insights into the PBAT degradation manner in ecosystems.

Exploring barium-titanium-peroxo-hydroxide as an excellent single-source precursor for crystallographically diverse barium titanate ceramics – parametric study

Barium-titanium-peroxo type amorphous materials gained importance with the advent of wet-chemical methods for the production of crystalline perovskite barium titanate (BaTiO3) electroceramics. In this paper, the chemical nature of the barium-titanium-peroxo precursor was determined by means of elemental (EPMA), spectroscopic (FT-IR and FT-Raman), XRD and thermal (DSC and TGA/DTA) analyses. Several synthesis parameters such as the barium source, the peroxide treatment time, the reaction temperature and the reaction time were investigated. The precursor was also thermally treated at varying temperatures between 30 °C and 1000 °C. Relatively high reaction temperatures are detrimental to the Ba∙O∙Ti structure, resulting in plain TiO2 formation. Though relatively low temperatures (ice bath) are needed to suppress unwanted TiOCl2, ambient synthesis conditions and short reaction time (2 h) resulted in the desired single-source properties, i.e. amorphous Ba∙O∙Ti-peroxo structure with Ba/Ti ratio of unity (1.04 ± 0.04). The addition of an extra stirring step during H2O2 addition lowered the chance of carbonate incorporation in the precursor. Thermal analysis under air and nitrogen atmosphere was performed and a stoichiometric formula of Ba2,08Ti2O(O2)1,9(OH)5,3∙3,1H2O was calculated, which was in very good agreement with literature data. The barium-titanium-peroxo-hydroxide material proved to be an excellent single-source precursor. Phase-pure, highly crystalline and facetted, stoichiometric BaTiO3 particles with differently crystallographically oriented facets were obtained via the molten-salt solid-state method ({100} or {111} oriented facets) as well as the hydrothermal route ({100} oriented facets).

Study on the dynamic characteristics and control strategies of the coupled system of the FHR and SCO2 cycle

The supercritical carbon dioxide (SCO2) Brayton cycle has high efficiency, compactness, and rapid response. Furthermore, the fluoride-salt-cooled high-temperature reactor (FHR), as a Generation IV nuclear reactor, is characterized by compactness, high temperature, and inherent safety. Therefore, the SCO2 cycle as the energy conversion system of the FHR can meet the requirements of modularity and compactness. However, the interaction characteristics between the FHR and SCO2 cycle are unknown, and the system control strategies that can guarantee the safety and flexibility of the coupled system need to be explored. In this study, a dynamic simulation model of the coupled system of the FHR and SCO2 cycle is established. Considering the complexity of the system, the dynamic characteristics of the FHR and SCO2 cycle are investigated separately. Then, the FHR and SCO2 cycle is coupled, and the interaction characteristics between the FHR and SCO2 cycle are further analyzed. It is shown that the coupled system is more flexible under SCO2 mass flow rate disturbance than under FHR reactivity disturbance. Based on that, various SCO2 mass flow rate control strategies are designed and investigated. Among them, the turbine bypass control strategy is the fastest, and system parameters are the most stable.

An ultra-durable ZIT glass-ceramic composite for immobilization of radioactive mixed lanthanide oxides

Zinc Titanate (ZIT) glass-ceramic composite is a potential candidate waste form for immobilizing radioactive lanthanide oxides due to its relatively high lanthanide embedding capacity and low reaction temperature. However, the composition of lanthanide oxides after electrolytic refining is very complex and the immobilization mechanism of lanthanide oxides by ZIT composite is not clear. Herein, we prepared ZIT-PrEu glass-ceramic waste forms by a solid-phase sintering method at 1200 °C for 4 h using mixed lanthanide oxides of Pr6O11 and Eu2O3 simulated as radioactive waste. The XRD and SEM results show that different mixed lanthanide oxide ratios have very little effect on the composition and microstructure of ZIT-PrEu waste forms with different waste embedding rates. With the increase of waste embedding rate, the density of the ZIT-PrEu glass-ceramic waste forms with different mixed lanthanide oxide ratios first increases and then decreases. When the embedding rate increases to 25 wt.%, the density of ZIT-PrEu waste forms with different mixed lanthanide oxide ratios reaches a maximum. The ZIT-PrEu glass-ceramic waste forms embedded with 25 wt.% waste exhibit excellent chemical durability, and the leaching rates of Pr ion and Eu ion are only 10-6 - 10-7 g·m-2·d-1 after 28 days at 90 °C. Moreover, the phase evolution of the ZIT composites immobilizing lanthanide oxides at different temperatures is revealed by XRD and FT-IR measurements. The lanthanides (Ln) are mainly present in the form of LnPO4 monazite phases.

Simulation analysis of gas-solid two-phase flow and reaction in a novel catalytic cracking reactor

A gas-solid two-phase flow reaction model was developed to evaluate the performance of a novel catalytic cracking reactor in the residue-to-chemicals (RTC) process. Coupled TFM, EMMS drag, and 12-lump kinetic models were employed to simulate the flow reaction process. The reaction temperature and product yields at the reactor exit aligned well with real industrial RTC reactor test results, indicating the reliability and effectiveness of the coupling model. Catalyst particles formed an internal circulation structure in the reactor, increasing the instantaneous catalyst-to-oil ratio. The reactor exhibited low axial and radial temperature gradients with higher reaction temperatures, accelerating the catalytic cracking rate and enhancing the selectivity for high-value products. The effects of the catalyst-to-oil ratio, catalyst inlet temperature, and feedstock mass flow rate on the flow reaction process were optimized. Results showed that both the catalyst-to-oil ratio and catalyst inlet temperature influenced the overall catalyst velocity distribution. Within the limit range, increasing the catalyst-to-oil ratio increased feedstock conversion, gasoline, LPG, dry gas, and coke yields, but decreased diesel yield. Conversely, increasing the feedstock mass flow rate showed opposite trends. Different trends in product yields were observed with varying inlet catalyst temperatures, with optimal product distribution at 973.15 K.

Numerical analysis of the ignition and gas-phase flame evolution of pulverized coal based on online experimental diagnostics

A transient ignition model employing a reduced chemical mechanism was developed to investigate the ignition characteristics and the gas-phase flame evolution of pulverized coal particles. The chemical percolation devolatilization (CPD) model was chosen to simulate the devolatilization process, and its accuracy was validated using a high-temperature entrained-flow reactor. Additionally, a novel method was introduced to cross-validate the single-particle simulation results with real-time OH-PLIF experimental measurements of particle streams, particularly at a large particle spacing ratio. The ignition mode was determined using the ignition delay time and volatile burnout time. Results show that as the oxygen volume fraction increases from 5% to 50% at a temperature of 1800 K, the ignition mode transitions from homogeneous ignition (GI) to heterogeneous ignition (HI). Notably, the same ignition mode was observed regardless of whether GI was defined using gas-phase temperature or OH levels. In the homo-heterogeneous ignition mode, the gas-phase flame intensity, characterized by OH levels, increases rapidly, then decreases, and re-increases slightly. The sequence of gas-phase reactions initiates with volatile combustion, followed by the co-combustion of residual volatiles and newly generated CO, and culminates in the combustion of CO itself. Online experimental findings confirmed that CO originates from char oxidation. Throughout this process, the gas-phase flame front extends outward until the volatiles are consumed.

A Demonstration of the Risk-Informed NEI 18-04 Design Evaluation Model for the Modular High-Temperature Gas Reactor

Several advanced reactor designs are now under active development in the United States and elsewhere, promising sustainable solutions to the growing world energy needs. The designs currently being considered are quite diverse and different from the more established light water reactor technology that has dominated the operating commercial nuclear landscape. While advanced reactor concepts were first explored in the dawn of the nuclear age, they are now being reconsidered under the light of modern needs, and specifically, for their flexible operating conditions and inherent safety characteristics. In response, the U.S. Nuclear Regulatory Commission staff is moving forward with development of 10 CFR Part 53 rulemaking, which is a more risk-informed, technology-agnostic framework for licensing and regulating such new designs. The nuclear industry response to this regulatory initiative resulted in the technical report by the Nuclear Energy Institute, NEI 18-04 Revision 1, which provides an implementation roadmap of the risk-informed approach when defining the safety case for a new plant design. The implementation of this safety case may be a nontrivial exercise for an actual reactor design. This paper provides a demonstration of performing such an analysis for a representative advanced reactor. Public information from the General Atomics high-temperature gas reactor design was considered in this demonstration. The analysis workflow was facilitated with the FPoliSolutions’ proprietary Risk-Informed System Engineering (RISE) digital platform, a product that was presented in previous publications. RISE is one application of FPoli’s enterprise digital platform, which was created to facilitate orchestration of complex workflows leveraging recent technologies developed at national laboratories, such as Idaho National Laboratory’s RAVEN and EMRALD frameworks. The analysis described in the paper includes the selection and classifications of events, the integration of probabilistic risk analysis artifacts, and event modeling simulations for consequence evaluations. The results are then used for system, structures, and components safety classification and a synthesis of the safety case for the design in line with the frequency-consequence targets presented in NEI 18-04. The purpose of the analysis, as framed in RISE, is to readily produce outputs and views that can aid users and regulators in making risk-informed decisions to demonstrate their plant safety case.

A Robust Synthesis of Co2P and Ni2P Nanocatalysts from Hexaethylaminophosphine and Phosphine-Enhanced Phenylacetylene Hydrogenation.

Metal-rich phases of general formula M2P have demonstrated interesting catalytic activity, e.g., for hydrogen evolution reaction and for hydrogenations in colloidal suspension. The production of well-crystallized nanoparticles of the M2P phase from commercial precursors on a large enough scale is not trivial as the existing routes generally require fairly high reaction temperatures and a large excess of the phosphorus source. Here, we selected a commercial aminophosphine, P(NEt2)3, as the phosphorus precursor (3 equiv or less) to develop a robust synthesis from CoCl2 (respectively NiCl2) that provided crystalline Co2P (respectively Ni2P) nanoparticles with high yields on a 9 mmol scale. Moreover, modification of the M2P nanoparticles via the addition of a molecular Lewis base is a promising route to trigger catalytic activity of the colloidal suspension at a lower temperature. For the hydrogenation of phenylacetylene catalyzed by Co2P and Ni2P nanoparticles, we showed that catalytic amounts of adequate phosphines, such as PnBu3 and also, in some instances, oleylamine, triggered a full conversion at lower temperatures than with the nanoparticles alone. We delineated the most efficient phosphines in the case of a Ni2P catalyst, using a stereoelectronic map of 13 phosphines.

Toward Methanol Production by CO2 Hydrogenation beyond Formic Acid Formation.

ConspectusThe Paradigm shift in considering CO2 as an alternative carbon feedstock as opposed to a waste product has recently prompted intense research activities. The implementation of CO2 utilization may be achieved by designing highly efficient catalysts, exploring processes that minimize energy consumption and simplifying product purification and separation. Among possible target products derived from CO2, methanol is highly valuable because it can be used in various chemical feedstocks and as a fuel. Although it is currently produced on a plant scale by heterogeneous catalysis using a Cu/ZnO-based catalyst, a limited theoretical conversion ratio at high reaction temperatures remains an issue. In addition, a catalytic system that can be adjusted to accommodate a variable renewable energy source for the synthesis of methanol is more desirable than current continuous-operation systems, which require a reliable energy supply. Recently, significant progress has been made in the field of homogeneous catalysis, which primarily relies on an indirect route to synthesize methanol via the hydrogenation of carbonate or formate derivatives in the presence of additives and solvents. However, homogeneous catalysis is inappropriate for industrial-scale methanol production because of the inefficient separation and purification processes involved.In this Account, we demonstrate a novel approach for methanol production under mild reaction conditions by CO2 hydrogenation catalyzed by multinuclear iridium complexes under heterogeneous gas-solid phase conditions without any additives and solvents. One of the aims of this Account provides insights for overcoming the barriers for efficient CO2 hydrogenation by focusing on catalyst design, specifically by incorporating varying functionalities into the ligand. The fundamental strategy entails activating hydrogen molecule and enhancing the hydricity of the resulting metal-hydride species, which is based on the following two concepts of catalyst design: (i) Activating a metal-hydride by electronic effects; and (ii) accelerating H2 heterolysis. We have elucidated the mechanism for accelerating H2 heterolysis using a state-of-the-art catalyst that contains an actor-ligand that responds to or participates in catalysis as opposed to a classical spectator-ligand.We have also demonstrated a novel heterogeneous catalysis using a molecular catalyst as a key step for the hydrogenation of CO2 to methanol beyond formic acid formation. The dehydrogenation of formic acid as a reverse reaction of formic acid hydrogenation is strongly favored in acidic aqueous solution. To circumvent the equilibrium limitation, we have envisioned an alternative route that both prevents the liberation of formic acid into the reaction medium, and develops a multinuclear complex to facilitate the transfer of multiple reactive hydrides. The unconventional gas-solid phase catalysis is capable of preventing the liberation of formate species and promoting further hydrogenation of formic acid through multihydride transfer.This novel catalytic system, which is the fusion of a molecular catalyst in heterogeneous catalysis, provides high performance for methanol synthesis through a sophisticated catalyst design and straightforward separation processes. A detailed mechanistic analysis of molecular catalysts in the gas phase would lead to significant progress in the field of Surface Organometallic Chemistry (SOMC).