Water Gas Shift Research Articles

Optimizing reverse water gas shift catalysis: Minimizing metal loading and enhancing performance with Pt/ZrO2 catalysts through Rh incorporation

In this study, the optimization of catalysts for the reverse water gas shift reaction by minimizing metal loading and enhancing the performance of supported Pt catalysts through Rh incorporation was done. The catalysts were synthesized by the wet impregnation method, in which the metal noble load in bimetallic samples decreased by approximately one-third compared to the reference platinum catalyst, with varying Rh-Pt ratios. In all materials, m-ZrO2, obtained by the hydrothermal method, was used as support. In the catalytic tests in a continuous packed-bed flow reactor at atmospheric pressure, all samples were active to catalyze CO2 reduction between 200 and 300 °C. Bimetallic samples, particularly those with an Rh-Pt atomic ratio of 20–80, exhibited superior performance in the RWGS reaction despite their lower metal content. Based on the results of H2-TPR, FTIR in situ, and XPS, we propose that the enhanced CO production in bimetallic samples compared to Pt/ZrO2 catalysts can be attributed to Rh increasing the reduction extent of supported Pt. This enhancement facilitates the hydrogenation of bicarbonate species into formate species, which subsequently evolve into Pt0-CO and ultimately into CO. Additionally, Rh incorporation enables an alternative pathway for CO generation, where Pt0-carbonyls, known for their CO-producing capability, are formed via CO2 dissociation on the Pt0 surface. However, higher Rh concentrations favor the CO2 methanation rather than the RWGS reaction.

Synthesis of Ni–FeCeO2 by mechanochemical method for high-temperature water-gas shift reaction

Hydrocarbon fuels have caused significant environmental damage, leading to a search for renewable alternatives like hydrogen. The water-gas shift reaction (WGSR) is a key process in hydrogen production, especially in ammonia synthesis. Typically, WGSR occurs in two stages: low-temperature (LT-WGSR) at 180–250 °C and high-temperature (HT-WGSR) at 310–450 °C. Traditional HT-WGSR catalysts use Fe–Cr, but the presence of carcinogenic hexavalent chromium (Cr6+) poses environmental risks, necessitating safer alternatives. This study explores the replacement of chromium with aluminum (Al) and cerium (Ce) in Fe-based catalysts, synthesized via mechanochemical methods. Characterization revealed that Fe–Ce catalysts (85:15 ratio) exhibited superior thermal stability. Additionally, varying nickel (Ni) contents were tested to improve activity, with 10% Ni offering the best performance despite some methane by-products. The study also examined the impact of reduction and calcination temperatures, GHSV, and steam/gas ratios on the catalyst's efficiency.

Pt-supported on N-doped carbon/TiO2 nanomaterials derived from NH2-MIL-125 for efficient photo-thermal RWGS reaction

To mitigate carbon dioxide (CO2) emissions and advance carbon neutrality, the conversion of CO2 into value-added fuels and chemicals via the reverse water–gas shift (RWGS) reaction is recognized as a promising approach. In this study, we designed platinum (Pt)-loaded nitrogen-doped carbon composite dual-phase titanium dioxide (TiO2) nanomaterials to achieve efficient photo-thermal performance in the RWGS reaction. The incorporation of Pt, nitrogen doping, and the selection of an appropriate calcination temperature enhance light responsiveness and reduce the recombination of photo-generated carriers, thereby improving the efficiency of the photo-thermal RWGS reaction. The optimized catalysts exhibited a high CO2 conversion (42.79 %), a carbon monoxide (CO) production rate (81.46 mmol gcat−1 h−1) and over 99.9 % selectivity under conditions of 400 °C and 1.2 W cm−2 light illumination. In addition, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) analyses revealed that Pt/TiO2@CN-525 was enriched with more oxygen defects, which was facilitate the adsorption and activation of CO2. CO temperature-programmed desorption (CO-TPD) showed that Pt/TiO2@CN-525 possesses a strong desorption capacity for CO. In addition, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) pointed to COOH* as a key intermediate in the reaction process. The photo-thermal co-catalyzed CO2 reduction by CO-TPD as well as in-situ DRIFTS indicated that Pt/TiO2@CN-525 follows the RWGS reaction. This work provides a potential strategy for the synthesis of catalysts for enhancing photo-thermal co-catalyzed RWGS reactions.

Pivotal copper bimetallic oxide in hierarchical Calcium magnesium materials for low-temperature carbon capture and utilization

Carbon removal from anthropogenic greenhouse gas emissions is essential to achieve net-zero emissions and mitigate climate change, and integrated carbon capture and utilisation (ICCU) has been studied for subsequent in-situ chemical production. However, high temperature and CaO sintering remain critical issues, highlighting the need for improved, low-cost CO2 adsorbents that can be regenerated at lower temperatures. Herin, we innovatively introduce the low-temperature ICCU coupled with reverse water gas shift reactions (RWGS) using dual functional materials (DFMs), exemplifying a range of potential transition metals doped over CaO with or without the MgO support. Among all the prepared DFMs, D-Cu showed desirable enhanced catalytic activity at a comparatively low-temperature performance (550°C) and still maintained a stable CO2 capture capacity (7.0mmol g−1) and CO yield (8.0mmol g−1) with an exceptional CO2 conversion (94.4 %) and CO selectivity (97.6 %) after cyclic hydrogenation. The mechanism study revealed that Ca2CuO3 bimetalliccatalyst in the hierarchical porous 2CaO/MgO matrix of D-Cu plays a crucial role in retaining its cyclic stability, surpassing that of noble D-Pt. Given the ICCU-RWGS performance and cyclic stability of cost-effective D-Cu at reduced operating temperatures, the findings would minimise energy and cost consumption.

Membrane reformer technology for sustainable hydrogen production from hydrocarbon feedstocks

Hydrogen (H2) is receiving growing interest as a clean energy carrier as the world’s energy system transitions towards net zero. Today, H2 is primarily produced from hydrocarbons using the steam methane reforming (SMR) process. This well-established method converts methane-rich gas into syngas, which is further treated with steam to increase H2 yield via the water-gas-shift (WGS) process. However, this conventional route results in high carbon intensity of 10 tons CO2/ton of H2. Therefore, there is a growing need for sustainable H2 production technologies that utilize existing fossil energy sources and infrastructure while minimizing carbon emissions and costs.Membrane reactors (MR) are a promising technology for sustainable H2 production from hydrocarbons. A H2-selective palladium-alloy (Pd–Au) membrane is integrated within the catalyst bed, creating a system where H2 production and separation occur simultaneously in a single unit. This integration offers several advantages over the conventional system; process intensification allows thermodynamic equilibrium conversion limitations to be overcome while producing high purity (>99%) H2 at milder operating temperatures of ∼550 °C compared to 800–1000 °C in conventional packed bed reactors. Downstream processes such as WGS reactors and pressure swing adsorption are eliminated, resulting in reduced capital and operating costs. Moreover, the by-product stream remains pressurized at 25–40 bar and contains CO2 at concentrations above 60%, enabling CO2 capture at reduced cost.

Impact of the K and Fe insertion methods in KFeCeZr catalysts on the CO2 hydrogenation to C2/C3 olefins at room pressure

Light olefins, traditionally sourced from petroleum, are currently being investigated through alternative routes, such as CO2 hydrogenation, aligning with CCUS policies. Alkali-promoted Fe-based catalysts have shown promise in coupling reverse water–gas shift and Fischer-Tropsch processes to produce light olefins from CO2 directly. The in-situ generated Fe5C2 phase is commonly associated with the high activity of these catalysts. However, the preparation methods employed can lead to distinct catalyst properties, which considerably impact the performance during the reaction. Here, we investigate different strategies to introduce K and Fe in the KFeCeZr system and correlate catalyst properties with catalytic activity during CO2 hydrogenation at ambient pressure. The catalyst prepared by one-pot precipitation of Fe, Ce, and Zr followed by K impregnation showed the most promising results in terms of conversion and productivity of light olefins. The effective incorporation of Fe in the CeZrOx structure during synthesis was essential for maintaining the high dispersion of metallic Fe particles after reduction, improving reactant chemisorption. Under reaction conditions, this catalyst showed the most remarkable propensity to form iron carbides (FexCy), mainly composed of Fe5C2 phase. In general, this work highlights the impact that the construction steps of a multifunctional catalyst have on the physicochemical properties and, consequently, on the catalytic activity.

Exergy Analysis of Hydrogen-Rich Syngas Production System Utilizing Palm Oil Empty Fruit Bunch using Pyrolysis Connected with Steam Methane Reformer

Fossil fuel consumption on a large scale continues to increase yearly, causing a shortage of energy sources. Hydrogen can help to overcome the shortage of energy sources. It can be produced from renewable energy sources, such as oil palm Empty Fruit Bunch (EFB) as biomass using pyrolysis processes equipped with steam methane reformer and water gas shift reactions. This research was conducted to determine the amount of hydrogen that can be produced and to analyze the exergy of the existing systems in the hydrogen production process. Aspen Plus has been used to design and analyze pyrolysis processes, steam methane reform, and water gas shift reactions. The results showed that when 6.54 kg Empty Fruit Bunch was used as raw material in a pyrolysis reactor, hydrogen could be produced in the amounts of 0.435 kg. The exergy values of raw materials and fuels are relatively high because the chemical exergy values of the compounds contained therein are also high. Based on the calculations, it is found that the combustion process is the process that experiences the most significant exergy destruction. The exergy efficiency of this hydrogen production process system is 22.77%.

Strong Metal-Support Interaction between Pt and TiO2 over High-temperature CO2 Hydrogenation.

The catalytic activities and stability of oxide-supported metal catalysts are significantly affected by metal-support interactions (MSI) between oxidic supports and supported metals. The surface properties of the support, such as its phase and defects, are crucial in MSI, including both the strong metal-support interaction (SMSI) and electronic metal-support interaction (EMSI). In this study, modulation of SMSI was achieved on rutile-supported Pt nanoparticles (NP) over high-temperature CO2 hydrogenation. The encapsulation of Pt NP surfaces with TiO2-x overlayers is precisely controlled by the defects. It is found that oxygen vacancy defects significantly enhance the catalytic stability of Pt/rutile under high-temperature reverse water-gas shift (RWGS) reaction by inhibiting the occurrence of SMSI. Pt/rutile with oxygen vacancies achieves a 301 molCO×gM-1×h-1 space time yield and considerably catalytic stability (decreased by 8%) at 800 °C over 100 h time-on-stream. Density functional theory (DFT) calculations suggest that the adsorption capacity of Pt NP on the rutile overlayer can be reduced by increasing electron density. Experimental results combined with DFT calculations show that electron transfer from Pt NP to rutile is reduced by the oxygen vacancy defects on Pt/R, preserving the metallic nature of Pt species during CO2 hydrogenation, thereby preventing the formation of SMSI.

Capture and catalytic conversion of CO2 from marine and offshore applications – A review

Abstract This contribution examines recent advances in modeling fluid dynamics and capture/conversion of CO2 from marine and offshore applications in packed-bed columns/trickle-bed reactors subjected to static inclination, externally-induced rolling and heaving motions. Breaking the axial symmetry of the two-phase flow once the packed bed system is tilted results in a significant decrease in process performance, the extent of which is determined by the magnitude of the tilt and the column/reactor diameter. Only the conversion of CO2 from marine engine emissions on-board large cargo ships via catalytic cycloaddition of CO2 to styrene oxide in multiphase large-diameter trickle-bed reactors increases slightly with increasing reactor inclination. Under the externally induced column/reactor oscillations, CO2 capture/conversion performance shifts toward the steady-state solution of the vertical column/reactor as the asymmetry between the two inclined positions decreases. Oscillating (between two inclined symmetrical positions) and heaving packed-bed columns/trickle-bed reactors generate an oscillating performance around the steady-state solution of the vertical static position, which is driven by the amplitude and period of the angular and heaving motions via the continuous evolution of the intensity of the reverse secondary flow and by the magnitude of the reactor/column diameter. The catalytic conversion of CO2 captured from marine emissions via an integrated process coupling reverse water-gas shift reaction and methanol synthesis in a fixed-bed reactors network system shows a remarkable enhancement with the addition of H2O adsorbent to the reaction systems in the sorption-enhanced process periods.

Effects of water injection on reaction temperature and hydrogen production in horizontal co-axial underground coal gasification

Underground coal gasification (UCG) is process of directly recovering energy as combustible gases such as hydrogen and carbon monoxide by combusting unmined coal resources in situ. During UCG process, the temperature in the gasification zone can exceed 1,300 °C, raising concerns about the potential melting of the steel pipe for oxidant injection. To control the temperature in the gasification zone, the use of water injection as an injection agent can be an option. Injecting water during UCG process serves two purposes: it decreases the temperature in the reaction zone by the endothermic effect of water, and it enhances the production of H2 by the reduction reaction of water. However, injecting excessive amounts of water may lead to a significant decrease in the temperature in the reaction zone, consequently cannot maintain the temperature range required for the UCG reaction. This study discusses the effects of water injection on the temperature of the gasification zone and the product gas by developing a chemical reaction model of UCG using COMSOL Multiphysics® software. The model was developed based on the temperature and produced gas results obtained from laboratory-scale artificial coal seam UCG experiments. Our findings reveal that water injection significantly influences the gasification process, controlling temperature in the reaction zone and promoting H2 production through steam gasification and water-gas shift reactions. Moreover, under the experiment and analysis conditions of this study, it is revealed that water injection up to an H2O/O2 molar ratio of 3.9 can effectively control the temperature of the gasification zone with enhancing H2 production.

Catalytic enhancement of water gas shift reaction with Cu/ZnO/ZSM-5: Overcoming challenges of CO2 and H2 rich feeds

Water gas shift (WGS) reaction commonly converts CO to CO2 using H2O and produces H2 and CO2 in a catalytic fixed bed reactor. This study aims to develop a Cu/ZnO/ZSM-5 catalyst loaded in water gas shift reactor for converting typical synthesis gas produced from dry reforming of methane (DRM) at medium temperature shift (MTS, 200–350 oC) conditions and for preventing reverse reaction due to high feed concentrations of CO2 and H2. The Cu/ZnO/ZSM-5 catalyst was prepared by impregnation method with lower Cu metal loading of 5, 10, and 15 wt%, respectively, compared to commercial catalysts. The synthesized catalyst was characterized using XRF, XRD, SEM, H2-TPR, NH3-TPD, and TGA. The catalyst activity and stability for the WGS reaction were tested in the fixed bed reactor at atmospheric pressure and temperature of 325 °C. The experimental results show that CO conversion increases with increasing Cu loading. The 15 wt% Cu/ZnO/ZSM-5 catalyst showed the best results with a CO conversion of 35% and a yield of H2 of 36% and showed good stability for 32 h. Based on the TGA, the 15 wt% Cu/ZnO/ZSM-5 catalyst forms a 0.04 g carbon/g catalyst, which is much lower when compared to commercial catalyst (0.105 g carbon/g catalyst). The relative activity of the synthesized catalyst indicates 2.4 times better when compared to commercial catalysts. High concentrations of H2 and CO2 in the feed may initiate side reactions, including reverse WGS, methanation, and carbon formation, which will decrease H2 yield.

Preparation of nano Cu-Mo2C interface supported on ordered mesoporous biochar of ultrahigh surface area for reverse water gas shift reaction

High conversion rate and selectivity are challenges for CO2 utilization through catalytic reverse water gas shift (RWGS) reaction. Herein, a novel mesoporous biochar (MB) supported Cu-Mo2C nano-interface was prepared by consecutive physical activation of coconut shells followed by carbothermal hydrogen reduction of bimetal. As compared with traditional carbon materials, this MB exhibited ultra-high specific surface area (2693 m2 g–1) and mesopore volume of mesopore (0.81 cm3 g–1) with a narrow distribution (2–5 nm), responsible for the high dispersion of binary Cu-Mo2C sites, CO2 adsorption and mass transfer in the reaction system. Moderate carbothermal reduction led to the sufficient reduction of Mo ion with carbon matrix of MB and dispersive growth of nano Cu-Mo2C binary sites (~ 6.1 nm) on the surface of MB. Cu+ species were formed from Cu0 via electron transfer and showed high dispersion with simultaneous boosted bimetal loading due to the strong interaction between nano Mo2C and Cu. These were advantageous to the intrinsic activity and stability of the Cu-Mo2C binary sites and their accessibility to the reactant molecules. Under the RWGS reaction conditions of 500 °C, atmospheric pressure, and 300,000 ml/g/h gas hour space velocity, the CO2 conversion rate over Cu-Mo2C/MB reached 27.74 × 10–5 molCO2/gcat/s at very low H2 partial pressure, which was more than twice that over traditional carbon supported Cu-Mo2C catalysts. In addition, this catalyst exhibited 99.08% CO selectivity and high stability for more than 50 h without a decrease in activity and selectivity. This study offers a new development strategy and a promising candidate for industrial RWGS.Graphical

High temperature pyrolysis of sewage sludge: Synergistic effects of co-pyrolysis with rice straw and composite plastics wastes

The synergistic effect of co-pyrolysis for the mixtures of sewage sludge (SS), rice straw (RS) and composite plastic wastes (PE&PP) has been investigated with the aim of high gas yields and hydrogen generation. In this context, the applicability of high temperature pyrolysis technology was evaluated at both rotary type batch reactor and rotating screw type continuous reactor operating under the industrially relevant conditions. Gas yields have been improved at increasing the operating temperatures up to 850 °C. The gas yield of 75.06 % with its H2 portion of 32.35 % has been achieved as the best results for continuous pyrolysis unit at pilot scale. Secondary reactions such as steam de-alkylation, steam cracking, water gas shift and so on were regarded as being responsible for the high gas yields when the primary products of pyrolysis, i.e. condensable vapors, were much exposed to the hot zones inside the reactor. The dehydration of organic components involving the loss of water may supply steam to create a reactive pyrolysis atmosphere. While the pyrolysis of sewage sludge and rice straw favors CO and CO2 formation due to the high oxygen contents of these feedstocks, more methane and light olefins were produced when the plastics were added to the feedstock blends. This was ascribed to the initially generated radicals from the decomposition of sewage sludge and/or rice straw that might promote the scission reactions of plastics towards volatiles. It was shown that high temperature pyrolysis can be applied to a variety of organic wastes such as rice straw, sewage sludge and waste plastics. Conversion of wastes to hydrogen fosters the circular economy by putting the disposal costs down and creates a new route on renewable hydrogen generation.

Governing chemical reactions and mechanisms of hydrogen generation during in-situ combustion gasification of heavy oil

The global push for sustainable energy solutions has highlighted the importance of producing carbon-zero hydrogen (H2) directly from petroleum reservoirs. In-situ combustion gasification (ISCG) presents a groundbreaking method to harness the potential of heavy oil reserves for clean hydrogen production. Although simulations have demonstrated the considerable promise of ISCG, the key reactions controlling hydrogen generation require experimental validation, and the underlying mechanisms remain largely unexplored. This research aims to describe the chemical reactions and mechanisms responsible for hydrogen generation during the ISCG of heavy oil. Using a specially designed kinetic cell, we conducted combustion and gasification experiments with heavy oil and coke. The findings revealed that clay minerals in the reservoir sand act as catalysts in the oxidation reactions of heavy oil by shifting reactions to lower temperatures by approximately 20 °C. Hydrogen production began at 450 °C and peaked at 900 °C, with coke gasification and the water-gas shift reaction being the primary mechanisms. Additionally, methane was produced due to hydrogen consumption via methanation reactions, and minerals in the reservoir sands were found to inhibit hydrogen production by increasing hydrogen consumption and methane generation at temperatures above 800 °C. Controlling the reservoir temperature within an optimal range between 450 and 800 °C can enhance hydrogen generation by managing the process mechanisms. This study provides a detailed examination of the ISCG process for heavy oil, paving the way for future development of kinetic models to simulate hydrogen production through ISCG. It also emphasizes the significance of mechanistic control in enhancing hydrogen generation and suppressing hydrogen consumption reactions.

Comparative Hydrogen Production Routes via Steam Methane Reforming and Chemical Looping Reforming of Natural Gas as Feedstock

Hydrogen production is essential in the transition to sustainable energy. This study examines two hydrogen production routes, steam methane reforming (SMR) and chemical looping reforming (CLR), both using raw natural gas as feedstock. SMR, the most commonly used industrial process, involves reacting methane with steam to produce hydrogen, carbon monoxide, and carbon dioxide. In contrast, CLR uses a metal oxide as an oxygen carrier to facilitate hydrogen production without generating additional carbon dioxide. Simulations conducted using Aspen HYSYS analyzed each method’s performance and energy consumption. The results show that SMR achieved 99.98% hydrogen purity, whereas CLR produced 99.97% purity. An energy analysis revealed that CLR requires 31% less energy than SMR, likely due to the absence of low- and high-temperature water–gas shift units. Overall, the findings suggest that CLR offers substantial advantages over SMR, including lower energy consumption and the production of cleaner hydrogen, free from carbon dioxide generated during the water–gas shift process.

CO2-selective membrane reactor process for water-gas-shift reaction with CO2 capture in a coal-based IGCC power plant

Integrated gasification combined cycle (IGCC) power plants enable pre-combustion carbon capture to reduce CO2 emissions. Membrane water-gas-shift (WGS) reactors can intensify these processes by converting raw syngas to H2 with simultaneous CO2 capture in one unit. This paper reports process design and techno-economic analysis (TEA) for a membrane reactor (MR) process with a CO2 selective ceramic-carbonate dual-phase (CCDP) membrane for WGS reaction with CO2 capture for a IGCC power plant. The target performance includes CO conversion > 95 %, hydrogen purity > 90 %, CO2 purity > 95 %, and carbon capture > 90 %. Using a commercial catalyst and a CCDP membrane, the MR can achieve the performance target at 750 °C and space velocity of 250 h−1. The outcome of the process design and TEA shows that the CCDP MR has an operating cost of $24 M/year, significantly lower than that for the conventional processes (40 M$/year). However, the MR process has a higher capital cost ($1007 M) than the conventional process ($527 M) because of the higher cost of the CCDP MRs. Modeling analysis shows a MR with higher CO2 permeance can deliver the target at a higher space velocity and lower membrane surface area to catalyst volume ratio, leading to a significantly reduced MR capital costs.

Reconfiguration of acid gas removal process matching the integration of coal chemical industry with green hydrogen

The focus of the acid gas removal process has shifted from decarbonization and desulfurization to desulfurization in the context of integrating coal chemical technology with green H2 without a water gas shift unit. The conventional Rectisol process, Selexol process, organic amine process, and sulfone-amine process have been reconfigured to form the R-Rectisol process, R-Selexol process, R-MDEA process, and R-Sulfolane-MDEA process to adapt to the shift of acid gas removal target. The removal efficiency of H2S and CO2, process energy consumption, and process cost are investigated to evaluate the technical and economic performance of the above four reconfigured acid gas removal processes. The results indicate that for the R-Recitsol process and R-Selexol process, both high pressure and low temperature increase the relative selectivity of H2S to CO2, thereby enhancing the selective removal of H2S. In contrast, for the R-MDEA process and R-Sulfolane-MDEA process, low pressure and low temperature improve the relative selectivity of H2S to CO2, thereby facilitating the selective removal of H2S. Under optimal operating conditions, the value of relative selectivity of H2S to CO2 of the R-Sulfolane-MDEA process is the largest, and the relative selectivity of H2S to CO2 of the R-Rectisol process, R-Selexol process and R-MDEA process are only 7.64 %, 12.85 %, and 68.40 % of the relative selectivity of H2S to CO2 of the R-Sulfolane-MDEA process, respectively. Compared to the other three reconfigured acid gas removal processes, the R-Sulfolane-MDEA process demonstrates superior advantages in both energy consumption and economic feasibility, provided that the H2S levels remain below 0.1 ppm in purified syngas. This study aims to enhance the decision-making process for gas purification methods in the coal chemical industry by considering integrated green H2 as an alternative to the water gas shift unit.

Constructing efficient Pd/Al2O3 catalyst for reverse water-gas shift via alkali-modification

The intrinsic nature of irreducible oxides (e.g. Al2O3) makes it hard to tune the charge state of supported late-transition metals, then difficult to adjust the selectivity of catalysts in CO2 hydrogenation. Herein, we find that modifying the Pd/Al2O3 catalyst with alkali metals (especially potassium) is efficient to boost the CO formation in CO2 hydrogenation. In comparison to Pd/Al2O3, approximately twenty-fold promotion in reverse water–gas shift (RWGS) rate was achieved on K-modified catalysts with proper K/Pd proportions. Combined structural characterizations demonstrate that the enhanced Pd-O interactions through K mediation stabilize the ca. 2 nm sized Pd particles as well as the electron-deficient state of Pd, which are robust enough during long-termed evaluation with undamped performance. In situ spectroscopy unveils a bi-dentate *HCOO associated reaction mechanism taking effect on alkali-modified catalysts, which contributes to ∼ 100 % of CO selectivity and 3318.1 mmol∙gPd-1∙h−1 of CO formation rate at 340°C.

In-Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water-Gas Shift Reaction.

In situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water-gas shift (RWGS) reaction. Surface oxygen atoms in various Mo-based catalysts are removed in H2-containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt-dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal -1 ⋅ h-1 at 600 °C has been achieved over in situ carbonized H-intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.

In‐Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water‐Gas Shift Reaction

AbstractIn situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water‐gas shift (RWGS) reaction. Surface oxygen atoms in various Mo‐based catalysts are removed in H2‐containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt‐dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal−1 ⋅ h−1 at 600 °C has been achieved over in situ carbonized H‐intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.