Hydrogenation Route Research Articles

Isotopic labelling of water reveals the hydrogen transfer route in electrochemical CO2 reduction.

Understanding the hydrogenation pathway in electrochemical CO2 reduction is important for controlling product selectivity. The Eley-Rideal mechanism involving proton-coupled electron transfer directly from solvent water is often considered to be the primary hydrogen transfer route. However, in principle, hydrogenation can also occur via the Langmuir-Hinshelwood mechanism using surface-adsorbed *H. Here, by performing CO2 reduction with Cu in H2O-D2O mixtures, we present evidence that the Langmuir-Hinshelwood mechanism is probably the dominant hydrogenation route. From this, we estimate the extent to which each mechanism contributes towards the formation of six important CO2 reduction products. Through computational simulations, we find that the formation of C-H bonds and O-H bonds is governed by the Langmuir-Hinshelwood and Eley-Rideal mechanism, respectively. We also show that promoting the Eley-Rideal pathway could be crucial towards selective multicarbon product formation and suppressing hydrogen evolution. These findings introduce important considerations for the theoretical modelling of CO2 reduction pathways and electrocatalyst design.

Investigation of Sn Promoter on Ni/CeO2 Catalysts for Enhanced Acetylene Semihydrogenation to Ethylene.

Ethylene, as an important chemical raw material, could be produced through the coal-based acetylene hydrogenation route. Nickel-based catalysts demonstrate significant activity in the semihydrogenation reaction of acetylene, but they encounter challenges related to catalyst deactivation and overhydrogenation. Herein, the effect of Sn promoter on Ni/CeO2 catalysts has been comprehensively explored for acetylene semihydrogenation. The optimized Ni/8%Sn-CeO2 catalytic performance was significantly improved, with 100% acetylene conversion and 82.5% ethylene selectivity at 250 °C, and the catalyst maintained high catalyst performance within a 1000 min stability test. A series of characterization tests show that CeO2 modified by moderate Sn4+ doping is more conducive to modulating the charge structure and geometry of the Ni active center. Additionally, the in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy and density functional theory results indicated that catalysts doped with Sn4+ facilitated more efficient desorption of ethylene from the catalyst surface compared to Ni/CeO2 catalysts, thus improving ethylene selectivity and yield. This study highlights an effective strategy for improving the catalytic performance of rare-earth-based catalysts through the incorporation of effective metal promoters.

Thermodynamic evaluation of solar energy-based methanol and hydrogen production and power generation pathways: A comparative study

Thermodynamic evaluation of solar energy-based methanol and hydrogen production and power generation pathways: A comparative study

Al2O3 Concentration Effect on Deep Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over NiWS/Al2O3-ZrO2 Catalysts.

The Al2O3 concentration effect over NiWS/Al x Zr100-x catalysts was investigated for deep hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene (4,6-DMDBT). The sol-gel method changed the wt % Al2O3 concentrations used to synthesize the Al x Zr100-x supports. The NiWS/Al x Zr100-x catalysts were prepared with ammonium metatungstate hydrate and nickel(II) nitrate hexahydrate by sequential incipient impregnation, calcination, and H2S/H2 activation. The catalytic evaluation data fit a pseudo-first-order trend in the 4,6-DMDBT HDS reactions. In the oxide phase, the catalysts presented Ni and W species in tetrahedral (td) and octahedral (oh) coordination, with the oh species prevailing as a function of the Al2O3 amount. The lower amount of Al2O3 can facilitate the "Type II" NiWS phase formation by weakening the interaction of the W-O-Al bond and promoting W and Ni species sulfidation. In the sulfide phase, catalysts with (oh) coordination and surface WO X species promote the formation of WS2 and NiWS species during the catalyst activation step. This species favors the reaction yield, where the hydrogenation route is predominant, with the highest initial reaction rate using the NiWS/Al25Zr75 catalyst. A direct correlation was found between high hydrogenation/hydrogenolysis ratio values and low Al2O3 concentrations.

Continuous Flow Synthesis of Furfuryl Ethers over Pd/C Catalysts via Reductive Etherification of Furfural in Ethanol

Furfural has become one of the most promising building blocks directly derived from biomass. It can be transformed into numerous important biobased chemicals. Among them, furfuryl ethers such as furfuryl ethyl ether (FEE) and tetrahydrofurfuryl ethyl ether (THFEE) are considered to be attractive derivatives, notably as fuel components, due to their high stability and high octane numbers. Therefore, the production of furfuryl ethers from furfural via a hydrogenation route is an important academic and industrial challenge and requires the deployment of new catalytic processes under green and competitive reaction conditions. The existing processes are based on a two-step process combining hydrogenation and reaction with a strong Bronsted acid catalyst in batch conditions. For the first time, a continuous flow one-step process has been elaborated for the conversion of furfural directly into furfuryl ethers based on reductive etherification. The present work explores the catalytic performance in a continuous flow of commercial palladium catalysts supported on activated carbon for the catalytic reductive etherification of furfural with ethanol in the presence of trifluoroacetic acid. The chemical and engineering aspects, such as the mechanisms and reaction conditions, will be discussed.

Pressure-induced generation of heterogeneous electrocatalytic metal hydride surfaces for sustainable hydrogen transfer

Metal hydrides are crucial intermediates in numerous catalytic reactions. Intensive efforts have been dedicated to constructing molecular metal hydrides, where toxic precursors and delicate mediators are usually involved. Herein, we demonstrate a facile pressure-induced methodology to generate a cost-effective heterogeneous electrocatalytic metal hydride surface for sustainable hydrogen transfer. Taking carbon dioxide (CO2) electroreduction as a model system and zinc (Zn), a well-known carbon monoxide (CO)-selective catalyst, as a model catalyst, we showcase a homogeneous-type hydrogen atom transfer process induced by heterogeneous hydride surfaces, enabling direct hydrogenation pathways traditionally considered “prohibited”. Specifically, the maximal Faradaic efficiency for formate is enhanced by ~fivefold to 83% under ambient conditions. Experimental and theoretical analyses reveal that unlike the distal hydrogenation route for CO2 to CO over pristine Zn, the Zn hydride surface enables direct hydrogenation at the carbon site of CO2 to form formate. This work provides a promising material platform for sustainable synthesis.

Pseudo-Jahn-Teller Effect Breaks the pH Dependence in Two-Electron Oxygen Electroreduction.

The hydrogenation of small molecules (like O2 and CO2) often exhibits strong activity dependence on pHs because of discrepant proton donor environments. However, some catalysts can show seldom dependence on two-electron oxygen electroreduction, a sustainable route of O2 hydrogenation to hydrogen peroxide (H2O2). In this work, a pH-resistant oxygen electroreduction system arising from the pseudo-Jahn-Teller effect is demonstrated. Thorough operando Raman spectra, local environment analyses and density function theory simulations, the lattice distortion of TiOxFy that introduces the pseudo-Jahn-Teller effect contributing to regulating local pHs at electrode-electrolyte interfaces and the absorption/desorption of key *OOH intermediate is revealed. Consequently, as comparison to 78.6% activity attenuation for common catalyst, the TiOxFy displays minor activity decay (3.2%) in the pH range of 1-13 with remarkable Faradaic efficiencies (93.4-96.4%) and H2O2 yield rates (595-614mgcm-2h-1) in the current densities of 100-1000mAcm-2. Further techno-economics analyses display the H2O2 production cost dependent on pHs, giving the lowest H2O2 price of $0.37kg-1. The present finding is expected to provide an additional dimension to pseudo-Jahn-Teller effect that leverages systems beyond traditional conception.

Simulation and conceptual design of an aniline production process from catalytic hydrogenation of nitrobenzene in ChemCAD

Aniline is a very important compound in organic chemistry, mainly used to synthesize polyurethane and its precursors. In the present work, the simulation and conceptual design of an aniline production process through the catalytic hydrogenation route of nitrobenzene was carried out using ChemCADÒ simulator. The simulated aniline production process consisted of a fired heater, a tubular reactor, several heat exchangers, a phase separator, a decanter, as well as two distillation columns. By means of the simulation, the temperatures, pressures, mass flowrates and enthalpies of the main intermediate and final streams were known, as well as the main operating and design parameters of some equipment. About 1,743 kg/h of aniline with a purity of 99.78% are produced at the top stream of the second distillation column, while about 49,881 kg/h of hydrogen are obtained as a by-product in the phase separator. In this work a first-of-its-kind ChemCAD simulation model was obtained in this work, which can be utilized for further optimization studies and tasks involving the increment of aniline purity, yields and productivity.

A Study on the Promoting Role of Renewable Hydrogen in the Transformation of Petroleum Refining Pathways

The refining industry is shifting from decarbonization to hydrogenation for processing heavy fractions to reduce pollution and improve efficiency. However, the carbon footprint of hydrogen production presents significant environmental challenges. This study couples refinery linear programming models with life cycle assessment to evaluate, from a long-term perspective, the role of low-carbon hydrogen in promoting sustainable and profitable hydrogenation refining practices. Eight hydrogen-production pathways were examined, including those based on fossil fuels and renewable energy, providing hydrogen for three representative refineries adopting hydrogenation, decarbonization, and co-processing routes. Learning curves were used to predict future hydrogen cost trends. Currently, hydrogenation refineries using fossil fuels benefit from significant cost advantages in hydrogen production, demonstrating optimal economic performance. However, in the long term, with increasing carbon taxes, hydrogenation routes will be affected by the high carbon emissions associated with fossil-based hydrogen, losing economic advantages compared to decarbonization pathways. With increasing installed capacity and technological advancements, low-carbon hydrogen is anticipated to reach cost parity with fossil-based hydrogen before 2060. Coupling renewable hydrogen is expected to yield the most significant economic advantages for hydrogenation refineries in the long term. Renewable hydrogen drives the transition of refining processing routes from a decarbonization-oriented approach to a hydrogenation-oriented paradigm, resulting in cleaner refining processes and enhanced competitiveness under emission-reduction pressures.

In-Situ Characterization Techniques for Mechanism Studies of CO2 Hydrogenation.

The paramount concerns of global warming, fossil fuel depletion, and energy crises have prompted the need of hydrocarbons productions via CO2 conversion. In order to achieve global carbon neutrality, much attention needs to be diverted towards CO2 management. Catalytic hydrogenation of CO2 is an exciting opportunity to curb the increasing CO2 and produce value-added products. However, the comprehensive understanding of CO2 hydrogenation is still a matter of discussion due to its complex reaction mechanism and involvement of various species. This review comprehensively discusses three processes: reverse water gas shift (RWGS) reaction, modified Fischer Tropsch synthesis (MFTS), and methanol-mediated route (MeOH) for CO2 hydrogenation to hydrocarbons. Along with analysing the reaction pathways, it is also very important to understand the real-time evolvement of catalytic process and reaction intermediates by employing in-situ characterization techniques under actual reaction conditions. Subsequently, in second part of this review, we provided a systematic analysis of advancements in in-situ techniques aimed to monitor the evolution of catalysts during CO2 reduction process. The section also highlights the key components of in-situ cells, their working principles, and applications in identifying reaction mechanisms for CO2 hydrogenation. Finally, by reviewing respective achievements in the field, we identify key gaps and present some future directions for CO2 hydrogenation and in-situ studies.

Flower-like hierarchical TS-1/Al2O3 composite supported NiMo catalysts for efficient hydrodesulfurization of dibenzothiophenes

Flower-like hierarchical TS-1/Al2O3 composite supported NiMo catalysts for efficient hydrodesulfurization of dibenzothiophenes

Synergistic engineering of palladium-cobalt nanoalloys on graphite sheet for efficient and sustainable hydrogen evolution reaction

Synergistic engineering of palladium-cobalt nanoalloys on graphite sheet for efficient and sustainable hydrogen evolution reaction

Towards the decarbonization of ammonia synthesis – A techno-economic assessment of hybrid-green process alternatives

Towards the decarbonization of ammonia synthesis – A techno-economic assessment of hybrid-green process alternatives

Hydrogenation of CO2 into Value-added Chemicals Using Solid-Supported Catalysts.

Reducing CO2 emissions is an urgent global priority. In this context, several mitigation strategies, including CO2 tax and stringent legislation, have been adopted to halt the deterioration of the natural environment. Also, carbon recycling procedures undoubtedly help reduce net emissions into the atmosphere, enhancing sustainability. Utilizing Earth's abundant CO2 to produce high-potential green chemicals and light fuels opens new avenues for the chemical industry. In this context, many attempts have been devoted to converting CO2 as a feedstock into various value-added chemicals, such as CH4, lower methanol, light olefins, gasoline, and higher hydrocarbons, for numerous applications involving various catalytic reactions. Although several CO2-conversion methods have been used, including electrochemical, photochemical, and biological approaches, the hydrogenation method allows the reaction to be tuned to produce the targeted compound without significantly altering infrastructure. This review discusses the numerous hydrogenation routes and their challenges, such as catalyst design, operation, and the combined art of structure-activity relationships for the various product formations.

Valorization of refinery flue gas through tri‐reforming and direct hydrogenation routes

AbstractThe rising amount of greenhouse gases has been contributing to global warming and, subsequently, climate change. Industries such as refineries and power plants emit a significant amount of CO2 into the atmosphere. It is imperative to curb anthropogenic CO2 emissions, and hence, in this effort, we explore the utilization of a refinery emission stream to produce value‐added chemicals. The chosen emission stream for the said purpose is a typical flue gas stream from refineries. Following the capture step, this CO2 stream has been leveraged for subsequent valorization processes. Two strategies have been proposed in this paper to valorize the captured carbon dioxide. The first strategy employs the tri‐reforming process with a refinery‐specific fuel gas stream as the co‐reactant. The resulting syngas from tri‐reforming has been converted to chemicals such as methanol (MET) and ethanol. Furthermore, to improve the amount of CO2 valorized, another approach with green hydrogen has been considered. The second strategy aims at direct hydrogenation of the captured CO2 stream to produce MET and ethanol. The proposed strategies analyze the feasibility of valorizing captured CO2 from flue gas to MET and ethanol in terms of gross margin per feed and percentage of CO2 valorization. The performance assessment and analysis of the proposed processes have been carried out using simulations in Aspen Plus® that exhibited up to 74% valorization of CO2 into valuable chemicals.

Selective hydrogenation of vanillin over a graphene-encapsulated nitrogen-doped bimetallic magnetic Ni/Fe@NDC nano-catalyst.

One of the main obstacles to the development of sustainable biomass feedstocks today is the research of selective hydrogenation of biomass platform compounds for the synthesis of high-value chemicals. This work reports on the synthesis of a Ni/Fe bimetallic catalyst with nitrogen-doped carbon serving as the carrier, hydrogen serving as the primary donor, and isopropanol serving as the reaction medium and serving as a secondary donor. Vanillin was catalytically hydrogenated to produce 4-methylguaiacol, a complete hydrogenation product, under a reaction temperature of 200 °C for four hours. A single product with a good yield (95.26% conversion and selectivity up to 99%) was achieved by the moderate conditions, offering a potential route for the catalytic hydrogenation of biomass platform compounds.

Optimizing islanded green ammonia and hydrogen production and export from Saudi Arabia

Optimizing islanded green ammonia and hydrogen production and export from Saudi Arabia

Technoeconomic analysis of photoelectrochemical hydrogen production from desalination waste brine using concentrated solar flux

Technoeconomic analysis of photoelectrochemical hydrogen production from desalination waste brine using concentrated solar flux

Palladium hydride promotion by KHCO3 enhances the decarboxylation rate

Palladium hydride promotion by KHCO3 enhances the decarboxylation rate

Optimization of catalyst activity and stability in the m-cresol hydrodeoxygenation through Ni particle size control

By taking advantage of different nanoparticle size control methodologies, the precise role of Ni particle size (from 1 nm to 9 nm) was evaluated in the HDO of m-cresol in vapor phase at 573 K under atmospheric pressure. The m-cresol HDO reaction pathways were found to be Ni-particle size dependent. The direct deoxygenation (DDO) rate increased by 10 times when decreasing Ni particle size from 9 nm to 1 nm, while the hydrogenation (HYD) and hydrogenolysis (HYG) rates moderately increased. By applying a geometric model, reaction rates were correlated to the different type of sites. Edges and corner sites (smaller particles) favor aromatics production (DDO route), while face sites (larger particles) favor both HYD and hydrogenolysis routes. Catalysts partially deactivated due to coke formation, with only slight sintering observed for 1 nm Ni particles. Such findings may serve in the further preparation of active and selective catalysts for bio-oils upgrading into fuel.