For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.

Constraints on Characteristics and Distribution of Gas Hydrate and Free Gas Using Broad-Band Processing of Three-Dimensional Seismic Data

Gas hydrate drilling expeditions in the Pearl River Mouth Basin,South China Sea,have identified concentrated gas hydrates with variable thickness.Moreover,free gas and the coexistence of gas hydrate and free gas have been confirmed by logging,coring,and production tests in the foraminifera-rich silty sediments with complex bottom-simulating reflectors(BSRs).The broad-band processing is conducted on conventional three-dimensional(3D)seismic data to improve the image and detection accuracy of gas hydratebearing layers and delineate the saturation and thickness of gas hydrate-and free gas-bearing sediments.Several geophysical attributes extracted along the base of the gas hydrate stability zone are used to demonstrate the variable distribution and the controlling factors for the differential enrichment of gas hydrate.The inverted gas hydrate saturation at the production zone is over 40% with a thickness of 90 m,showing the interbedded distribution with different boundaries between gas hydrate-and free gas-bearing layers.However,the gas hydrate saturation value at the adjacent canyon is 70%,with 30-m-thick patches and linear features.The lithological and fault controls on gas hydrate and free gas distributions are demonstrated by tracing each gas hydrate-bearing layer.Moreover,the BSR depths based on broad-band reprocessed 3D seismic data not only exhibit variations due to small-scale topographic changes caused by seafloor sedimentation and erosion but also show the upward shift of BSR and the blocky distribution of the coexistence of gas hydrate and free gas in the Pearl River Mouth Basin.

Analysis of Commuting Modal Shift in Consideration of Social Interaction of Consciousness for Environment

It is the matter for achievement of the low carbon transport system that the excessive use of private vehicles can be controlled appropriately.Not only improvement of service level of modes except private vehicle,but also consciousness for environmental problem of individual trip maker is important for eco-commuting promotion.On the other hand,consciousness for environment would be changed by influence of other person.Accordingly,it is aimed in the study that the structure of decision-making process for modal shift to the eco-commuting mode in the local city is described considering environmental consciousness and social interaction.For the purpose,the consciousness for the environment problem and the travel behavior of the commuter at the suburban area in the local city are investigated by the questionnaire survey.The covariance structure about the eco-consciousness is analyzed with the database of the questionnaire survey by structural equation modeling.As the result,it can be confirmed with the structural equation model that the individual environmental consciousness is strongly related with the intention of self-sacrifice and is influenced with the local interaction of the individual connections.On the other hand,the intention of modal shift for the commuting mode is analyzed with the database of the questionnaire survey.It can be found out that the environmental consciousness is not statistically significant for commuting mode choice with the present poor level of service of public transport.However,the intention of self-sacrifice for the prevention of the global warming is statistically confirmed as the factor of modal shift with the operation of eco-commuting bus service with the RP/SP integrated estimation method.As the result,the multi-agent simulation system with social interaction model for eco consciousness is developed to measure the effect of the eco-commuting promotion.For the purpose,the carbon dioxide emission is estimated based on traffic demand and road network condition in the traffic environment model.On the other hand,the relation between agents is defined based on the small world network.The proposed multi-agent simulation is applied to measure the effect of the eco-commuting promotion such as improvement of level of service on the public transport or education of eco-consciousness.The effect of the promotion plan can be observed with the proposed multi-agent system.Finally,it can be concluded that the proposed multi-agent simulation with social interaction for eco-consciousness is useful for planning of eco-commuting promotion.

Hydrate capture CO_2 from shifted synthesis gas, flue gas and sour natural gas or biogas

CO2 capture by hydrate formation is a novel gas separation technology, by which CO2 is selectively engaged in the cages of hydrate and is separated with other gases, based on the differences of phase equilibrium for CO2 and other gases. However. rigorous temperature and pressure, high energy cost and industrialized hydration separator dragged the development of the hydrate based CO2 capture. In this paper, the key problems in CO2 capture from the different sources such as shifted synthesis gas, flue gas and sour natural gas or biogas were analyzed. For shifted synthesis gas and flue gas, its high energy consumption is the barrier, and for the sour natural gas or biogas （CO2/CH4 system）, the bottleneck is how to enhance the selectivity of CO2 hydration. For these gases, scale-up is the main difficulty. Also, this paper explored the possibility of separating different gases by selective hydrate formation and reviewed the progress of CO2 separation from shifted synthesis gas, flue gas and sour natural gas or biogas.

Reverse water gas shift reaction over Co-precipitated Ni-CeO_2 catalysts

The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.

Catalytic Reduction of CO2 to CO via Reverse Water Gas Shift Reaction:Recent Advances in the Design of Active and Selective Supported Metal Catalysts

The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.

Effect of Mg/Al atom ratio of support on catalytic performance of Co-Mo/MgO-Al_2O_3 catalyst for water gas shift reaction

Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO（x）-Al2O3 catalyst and the contents of Mo^5＋, Mo^4＋, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.

A Novel γ-Alumina Supported Fe-Mo Bimetallic Catalyst for Reverse Water Gas Shift Reaction

In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.

Downward shift of gas hydrate stability zone due to seafloor erosion in the eastern Dongsha Island,South China Sea

New acquired and reprocessed three-dimensional(3D)seismic data were used to delineate the distribution and characterization of bottom simulating reflections(BSRs)in the Chaoshan Sag,in the eastern part of Dongsha Island,South China Sea.Three submarine canyons with different scales were interpreted from the 3D seismic data,displaying three stages of canyon development and are related with the variation of BSR.Abundant faults were identified from the coherence and ant-tracing attributions extracted from 3D seismic data,which provide the evidence for fluid migration from deeper sediments to the gas hydrate stability zone(GHSZ).The uplift of Dongsha Island created a large number of faults and leads to the increased seafloor erosion.The erosion caused the cooling of the seafloor sediments and deepening of the base of the gas hydrate stability zone,which is attributed to the presence of paleo-BSR and BSR downward shift in the study area.Hence,methane gas may be released during the BSR resetting and gas hydrate dissociation related with seafloor erosion.

Ceria modified three-dimensionally ordered macro-porous Pt/TiO_2 catalysts for water-gas shift reaction

Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy（SEM）, X-ray diffractometer（XRD）, high-resolution transmission electron microscopy（HRTEM） and temperature programmed reducfion（TPR） techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift （WGS） reaction in a wide temperature range （180-360 ℃）. The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.

Boosting the water gas shift reaction on Pt/CeO_(2)-based nanocatalysts by compositional modification: Support doping versus bimetallic alloying

The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.

Promotion effect of Re additive on the bifunctional Ni catalysts for methanation coupling with water gas shift of biogas: Insights from activation energy

The cheap manganese sand was first modified by H2O2 and was further creatively utilized as Ni-based catalyst support.In order to enhance the catalytic performance,Re was added into the Ni-based catalyst and the promotion effect of Re on the methanation coupling with water gas shift of biogas was investigated from the perspective of activation energy.It was found that CH4 and CO2 formation rates,which separately represented the reaction rate of methanation and water gas shift,were both enhanced after Re addition compared to non-added catalyst.Two kinetics models including empirical model and K-model were employed and from the results of calculation,it showed that Re selectively decreased the activation energy of methanation reaction and had little impact on the activation energy of water gas shift.The increased CO2 formation rate was owing to the assistance of accelerated H2O production from methanation rather than the activation energy change in water gas shift.

Monolithic macroporous catalysts—a new route for miniaturization of water-gas shift reactor

Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic catalysts were applied to water gas shift （WGS） reaction in reformed gases. The SEM and TEM results indicated that the monoliths possessed macroporosity, and that the platinum particles homogeneously dispersed on the supports with the particle size in the range of 1-2 nm. The reducibility of the catalysts was characterized by TPR method, and it was shown that the monolithic PtOx/CeO2/Al2O3 exhibited the similar reducibility property to that of the particle PtOx/CeO2 reported in literatures. The CO conversion over the monolithic catalysts is higher than that over micro-reactor catalysts for WGS reaction in the reformed gases conditions, indicating that the monolithic macroporous catalysts is a potential new route for miniaturization of WGS reactor.

Activity promotion of anti-sintering Au■MgGa_2O_4 using ceria in the water gas shift reaction and catalytic combustion reactions

Heterogeneous gold nanocatalysts have both inspired researchers with their unique catalytic performance and frustrated them due to the contradictions observed in their activities and stabilities.A recent breakthrough has shown that gold nanoparticles(NPs)can retain their catalytically active size over a MgGa2O4 spinel support upon sintering at high temperatures.Herein,we report the catalytic activity of anti-sintering AuGMgGa2O4 for use in water gas shift reaction(WGSR)and catalytic combustion reactions,and the promoting effect of ceria.Upon adding ceria to 800℃-aged AuGMgGa2O4,the CO conversion in the WGSR was increased from ~1.5% to ~34.0% at 450 ℃,and the “light-off” temperatures(T50)for methane combustion and CO oxidation were decreased by ~80 and ~100 ℃,respectively.Characterizations using XRD,HAADF-STEM,EDS mapping,H2-TPR,XPS,and DRIFTs confirmed the proximate contact of Au with ceria and their significant synergistic effect,which thereby combined the benefits of ceria toward the dissociation of H2O or O2 and the Au NPs toward activating CO or CH4.These results show that this stepwise stabilization-activation strategy is efficient for rationally constructing stable and active gold nanocatalysts,which may open up possibilities for the wide application of gold nanocatalysts at elevated temperatures.

Model for Reduction of Iron Oxide Pellet with a C-O-H-N Gas Mixture Considering Water Gas Shift Equilibrium in the Gas While It Diffuses through the Product Layer

In metallurgical processes, more and more usage of hydrocarbons is encouraged to bring down the carbon emissions. In this regard, numerous investigations on reduction of oxides by C-O-H-N gas mixture have been reported. Attempts to simulate these reduction processes using shrinking core model, one of the common models used for such studies, have under predicted the reduction rates. This may be owing to the fact that the homogeneous reaction in the gas phase is not being considered. If the reaction temperatures are above 1,000 K, generally so for many reduction processes, the homogeneous gas reaction rates are expected to be high enough that local equilibrium in the gas phase can be assumed. In the present study, reduction of wustite in a C-O-H-N gas mixture has been modeled using shrinking core model considering the water gas shift equilibrium in the gas while it diffuses through the product layer.

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.

Computational Screening of Pt1@Ti_(3)C_(2)T_(2)(T=O,S)MXene Catalysts for Water-Gas Shift Reaction

Single-atom catalysts(SACs)provide an oppor-tunity to elucidate the catalytic mechanism of complex reactions in heterogeneous catalysis.The low-temperature water-gas shift(WGS)reaction is an important industrial technology to obtain high purity hydrogen.Herein,we study the catalytic activity of Pt1@Ti_(3)C_(2)T_(2)(T=O,S)SACs,where one subsurface Ti atom with three T vacancies in the functionalized Ti_(3)C_(2)T_(2)(T=O,S)MXene is substituted by one Pt atom,for the low-temperature show that Pt1@Ti_(3)C_(2)T_(2)provides an excellent platform for the WGS reaction by its bowl-shaped vacancy derived from the Pt1 single atom and three T defects surrounding it.Especially,Pt1@Ti_(3)C_(2)S_(2)SAC has higher catalytic performance for the WGS reaction,due to the weaker electronegativity of the S atom than the O atom,which significantly reduces the energy barrier of H*migration in the WGS reaction,which is often the rate-determining step.In the most favorable redox mechanism of the WGS reaction on Pt1@Ti_(3)C_(2)S_(2),the rate-determining step is the dissociation of OH*into O*and H*with the energy barrier as low as 1.12 eV.These results demonstrate that Pt1@Ti_(3)C_(2)S_(2)is promising in the application of MXenes for low-temperature WGS reactions.

Three-stage pyrolysis–steam reforming–water gas shift processing of household,commercial and industrial waste plastics for hydrogen production

Five common single plastics and nine different household,commercial and industrial waste plastics were processed using a three-stage(i)pyrolysis,(ii)catalytic steam reforming and(iii)water gas shift reaction system to produce hydrogen.Pyrolysis of plastics produces a range of different hydrocarbon species which are subsequently catalytically steam reformed to produce H_(2)and CO and then undergo water gas shift reaction to produce further H_(2).The process mimics the commercial process for hydrogen production from natural gas.Processing of the single polyalkene plastics(high-density polyethylene(HDPE),low-density polyethylene(LDPE),and polypropylene(PP))produced similar H_(2)yields between 115 mmol and 120 mmol per gram plastic.Even though PS produced an aromatic product slate from the pyrolysis stage,further stages of reforming and water gas shift reaction produced a gas yield and composition similar to that of the polyalkene plastics(115 mmol H_(2)per gram plastic).PET gave significantly lower H_(2)yield(41 mmol per gram plastic)due to the formation of mainly CO,CO_(2)and organic acids from the pyrolysis stage which were not conducive to further reforming and water gas shift reaction.A mixture of the single plastics typical of that found in municipal solid waste produced a H_(2)yield of 102 mmol per gram plastic.Knowing the gas yields and composition from the single plastics enabled an estimation of the yields from a simulated waste plastic mixture and a‘real-world’waste plastic mixture to be determined.The different household,commercial and industrial waste plastic mixtures produced H_(2)yields between 70 mmol and 107 mmol per gram plastic.The H_(2)yield and gas composition from the single waste plastics gave an indication of the type of plastics in the mixed waste plastic samples.

A cross-cultural study of sustainable nutrition and its environmental impact in Asia and Europe:A comparison of China and Germany

Global challenges such as climate change,biodiversity loss,and health crises necessitate a shift towards sustainable diets.Incorporating sustainability into food-based dietary guidelines(FBDGs)is essential for this shift,and cultural considerations also play a vital role,as food culture significantly influences dietary habits.Considering that Asia and Europe exhibit distinct food cultures,tailored approaches are necessary.Additionally,countries face diverse nutritional challenges,ranging from malnutrition to diet-related diseases,and regional variation in environmental impact necessitates context-specific strategies.Achieving sustainable nutrition depends on understanding cultural influences and regional dynamics.This paper compares China’s and Germany’s dietary guidelines and dietary patterns and their impact on sustainability.It shows that Chinese and German FBDGs only slightly differ,despite the different eating cultures and habits of each country.Alone the recommended amounts for eggs and fish are considerably higher in China than in Germany.However,in both China and Germany,actual dietary patterns deviate from the dietary guidelines.In China,concomitant with economic growth and urbanization,a dietary shift towards increased consumption of animal products and decreased consumption of vegetables and cereals has been observed in the last decades,which has led to a decline in nutritional deficiencies but an increase in obesity and overweight.Obesity and overweight are also on the rise in Germany.A dietary shift could therefore also be beneficial for public health.While following the respective national guidelines would benefit the environment,alternative diets such as a plant-based diet offer even lower environmental footprint.Revising guidelines to prioritize sustainability in addition to health aspects while considering regional contexts and cultural preferences is recommended to foster sustainable eating habits globally.This approach is pivotal for promoting dietary shift towards sustainability on a global scale.

Desulfurization kinetics of ZnO sorbent loaded on semi-coke support for hot coal gas

Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp（-8.270×103/RgT） and Dep=1.262×10-4exp（1.522×104/RgT）.It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.