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.

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.

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.

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.

Effect of Addition Sequence during Neutralization and Precipitation on Iron-based Catalysts for High Temperature Shift Reaction

The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.

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.

Influence of Reaction Conditions on Methanol Synthesis and WGS Reaction in the Syngas-to-DME Process

A series of CuO-ZnO catalysts （with different Cu/Zn molar ratios） were prepared, and evaluated under the reaction conditions of syngas-to-dimethyl ether （DME） with three sorts of feed gas and different space velocity. The catalysts were characterized by X-ray diffraction （XRD） and temperatureprogrammed reduction （TPR）. The experiment results showed that the reaction conditions of syngas-to- DME process greatly affected the methanol synthesis and WGS reaction. The influence caused by Cu/Zn molar ratio was quite different on the two reactions; increasing of percentage of CO2 in feed gas was unfavorable for catalyst activity, and also inhibited both reactions; enhancement of reaction space velocity heavily influenced the performance of the catalyst, and the benefits were relatively less for methanol synthesis than for the WGS reaction.

Structure-activity relationship in water-gas shift reaction over gold catalysts supported on Y-doped ceria

The utilization of pure hydrogen as an energy source in fuel cells gave rise to renewed interest in developing active and stable water-gas shift catalysts. Gold catalysts have proven to be very efficient for water-gas shift reaction at low temperature. The aim of the present study was to investigate the effect of:(i) different preparation methods(impregnation and coprecipitation) to obtain a modified ceria support,and(ii) the amount of Y_2 O_3(1.0 wt%, 2.5 wt%, 5.0 wt% and 7.5 wt%) as dopant on the water-gas shift activity of Au/CeO_2 catalysts. An extended characterization by means of S_(BET), XRD, HRTEM/HAADF, FTIR,H_2-TPR and CO-TPR measurements in combination with careful evaluation of the catalyst behavior allowed to shed light on the parameters governing the water-gas shift activity. The catalysts show very high activity(>90% CO conversion) in the temperature range 180-220 ℃,with a slightly better performance of the gold catalysts on supports prepared by impregnation. The decreased activity with increasing Y_2 O_3 concentration is related to the hindering of oxygen mobility due to ordering of surface oxygen vacancies in vicinity of segregated Y^(3+). The effect of catalyst pre-treatments and the stability of the best performing samples were examined as well.

Adsorption Properties of Water Vapor on Iron Oxide Containing Cerium Oxide

The properties of adsorption of water vapor on iron oxide containing CeO 2 have been studied by pulse gas chromatography(GC) with the method of retention volume It was found that the adsorption heat of water vapor on the catalyst decreased and the number of adsorption centers did not change as the amount of cerium oxide increasing in the samples However, the adsorption heat increased somewhat as the sample contains enough amount of cerium oxide The activities of the samples catalyzing the water gas shift(WGS) reaction were measured The results showed that the lower the adsorption heat of a sample was, the higher its activity became It was proved that cerium oxide was a catalyst accelerator in the WGS catalysis

NiCe bimetallic nanoparticles embedded in hexagonal mesoporous silica (HMS) for reverse water gas shift reaction

Reverse water gas shift(RWGS)reaction is a crucial process in CO_(2)utilization.Herein,Ni-and NiCe-containing hexagonal mesoporous silica(Ni-HMS and NiCe-HMS)catalysts were synthesized using an insitu one-pot method and applied for RWGS reaction.At certain reaction temperatures 500-750℃,Ni-HMS samples displayed a higher selectivity to the preferable CO than that of conventionally impregnated Ni/HMS catalyst.This could be originated from the smaller NiO nanoparticles over Ni-HMS catalyst.NiCe-HMS exhibited higher activity compared to Ni-HMS.The catalysts were characterized by means of TEM,XPS,XRD,H_(2)-TPR,CO_(2)-TPD,EPR and N_(2) adsorption-desortion technology.It was found that introduction of Ce created high concentration of oxygen vacancies,served as the active site for activating CO_(2).Also,this work analyzed the effect of the H_(2)/CO_(2)molar ratio on the best NiCe-HMS.When reaction gas H_(2)/CO_(2)molar ratio was 4 significantly decreased the selectivity to CO at low temperature,but triggered a higher CO_(2)conversion which is close to the equilibrium.

程序升温碳化法一步合成Cu/β-Mo_(2)C催化剂及其RWGS反应性能研究

在逆水煤气变换(RWGS)反应中,Cu氧化物催化剂在高温下极易发生失活,而过渡金属碳化物具有分散和稳定Cu颗粒的作用。以七钼酸铵(AMT)、六次甲基四胺(HMT)和硝酸铜为原料,通过程序升温碳化法一步合成了Cu负载量(质量分数,下同)为1%、3%的Cu/β-Mo_(2)C催化剂,采用XRD、H_(2)-TPR、SEM和HRTEM进行了表征。结果表明,Cu的加入直接使β-Mo_(2)C的特征衍射峰变弱,说明金属与载体发生了强相互作用。低负载量的Cu在β-Mo_(2)C载体上以5 nm大小的纳米粒子均匀地分散,具有更多的活性中心。其中1%Cu/β-Mo_(2)C催化剂在600℃下的CO_(2)转化率和CO选择性分别为51.00%和100%;表观活化能为24.69 kJ/mol,低于3%Cu/β-Mo_(2)C,具有良好的活性和稳定性。研究证实1%Cu/β-Mo_(2)C具有良好的催化性能,是RWGS潜在的高效催化剂。

Catalytic performance of Co-Mo-Ce-K/γ-Al_(2)O_(3) catalyst for the shift reaction of CO in coke oven gas

The catalytic performance of Co-Mo-Ce-K/γAl_(2)O_(3) catalyst for the shift reaction of CO in coke oven gas is investigated using X-ray diffraction(XRD)and temperature-programmed reduction(TPR).The results indicate that Ce and K have a synergistic effect on promoting the catalytic activity,and the Co-Mo-Ce-K/γAl_(2)O_(3) catalyst with 3.0 wt-%CeO2 and 6.0 wt-%K_(2)O exhibits the highest activity.CeO2 favors Co dispersion and mainly produces an electronic effect.TPR characterization results indicate that the addition of CeO2-K_(2)O in the Co-Mo-Ce-K/γ-Al_(2)O_(3) catalyst decreases the reduction temperature of active components,and part of octahedrally coordinated Mo6+transforms into tetrahedrally coordinated Mo6+,which has a close relationship with the catalytic activity.

金负载量对低温水煤气变换Auα-Fe_2O_3催化剂结构和性能的影响

采用共沉淀法制备了低温水煤气变换Au α Fe2O3催化剂。通过正交实验优化催化剂的还原活化条件,考察了金负载量对催化剂性能的影响。采用BET、XRD、UV VIS、XRF、H2 TPR和O2 TPO等表征手段对催化剂的结构进行分析,并与其催化性能进行关联。结果表明,(1)采用10% H2 N2还原气将催化剂在150℃原位还原9h,其催化活性最高;(2)金的最佳负载量为8 00%,此时在催化剂制备过程中金的流失量较少,金粒子较小,也有利于抑制催化剂在反应过程中烧结;(3)TPR TPO结果表明,金的负载量为8 00%时,Au α Fe2O3催化剂具有较易被还原、不易被氧化的性质,从而显示出最高催化活性。(4)Au α Fe2O3催化剂中的金以单质金(Au0)形式存在;其高活性与Au0 Fe3O4间的协同作用有关。

钴钼基水煤气变换催化剂及其催化反应工艺

介绍了国内外CO变换催化剂的发展及其在不同变换工艺中的应用,阐述了Co-M o基催化剂的催化机理与硫化方法。通过综合分析中温变换、中温变换串联低温变换、中温变换串联两段低温变换和全程低温变换4种代表性的工艺流程,提出了高效节能型的全程低温变换工艺将是变换技术的发展方向,开发适应全程低温变换工艺的高活性和高稳定性的Co-M o基变换催化剂及其预硫化技术是今后的主要研究目标。

助剂对低温水煤气变换反应Au/α-Fe_2O_3催化剂性能的影响

采用共沉淀法制备了系列Au/α-Fe2O3-MOx(M=Zr、A l、Mg、Ca、Ba)催化剂,通过N2物理吸附、XRD、H2-TPR和CO2-TPD-MS等手段对催化剂的物化性质进行表征,考察了富氢下低温水煤气变换(WGS)反应中助剂对Au/α-Fe2O3催化剂性能的影响。结果表明,助剂ZrO2能有效提高Au/α-Fe2O3催化剂在富氢气氛下低温WGS反应活性和稳定性,反应温度150℃时CO转化率可达88.45%,且催化剂具有较高的稳定性。研究发现,添加ZrO2助剂能抑制载体晶粒的生长,降低载体晶粒度,提高催化剂的比表面积,改善催化剂的还原性能和表面酸碱度,从而提高催化剂的催化活性和稳定性。

低变催化剂还原性能研究

利用ＸＲＤ、ＴＰＲ和固定床反应装置对ＣｕＯ／ＺｎＯ／Ａｌ２Ｏ３低变催化剂还原过程进行了深入考察。结果表明，还原终止温度对还原后Ｃｕ的状态和催化剂活性起决定性作用，提高温度和还原气浓度可缩短还原时间；Ｈ２／Ｎ２的还原效果最好。同时发现还原反应存在着诱导期现象。

以水热法合成的ZrO_2负载Au催化剂上的低温水煤气变换反应

采用一种简便的水热法合成了一系列ZrO2,并采用沉积-沉淀法制得相应1.0%Au/ZrO2催化剂,在模拟甲醇重整气气氛下评价了它们的低温水煤气变换(WGS)反应催化性能.结果发现,于150oC水热合成的ZrO2负载的Au催化剂活性最佳,240oC反应时CO转化率达87%,明显高于相同反应条件下Au负载量较高的Au/Fe2O3,Au/CeO2及Au/CeZrO4催化剂.采用X射线衍射、原子吸收光谱、N2物理吸脱附及扫描电子显微镜等手段对样品进行了表征.结果表明,Au/ZrO2催化剂的总孔体积及平均孔径越大、圆形片状形貌越规整,其低温WGS催化活性就越高.

LB型节能催化剂上高温变换反应本征动力学及工业化测定

运用正交实验设计安排了LB型节能催化剂高温变换反应本征动力学实验,测得不同温度、不同流量、不同水碳比、不同反应气体摩尔分数下LB型节能催化剂上CO高温变换反应本征动力学数据。用甲酸盐机理模型和幂函数模型拟合实验数据,确定了本征动力学模型参数。进行了本征动力学模型统计检验,表明所建模型无论局部还是整体都是显著和可信的。在此基础上,进行了大型合成氨装置上LB型节能催化剂高变反应工业化测定,按多组分单一反应等温球形催化剂一维非均相反应-扩散模型,利用配置法结合解非线性方程组的Merson法求解模型,得到了工业反应器中催化剂床层温度、内扩散有效因子、CO转化率和摩尔分数随床层相对高度的分布,模拟结果与工业化测定结果吻合。

高温煤气脱硫及其对逆水煤气变换反应的影响

采用天然石灰石作脱硫剂,在固定床上进行高温煤气脱硫,研究脱硫剂粒径、用量、温度和入口H2S浓度对脱硫性能的影响及脱硫反应对逆水煤气变换反应的影响,并得到CaO的转化率曲线。结果表明:粒径对脱硫效果的影响很大,其中以0.38～0.9mm的石灰石脱硫效果最佳;脱硫剂用量增加,气固之间的接触机会增加,脱硫反应进行得更完全;温度对脱硫过程的影响比较复杂,最佳的脱硫温度为脱硫剂完全煅烧的温度;在一定的空速下,随着入口H2S浓度的减小,反应速率减慢;脱硫剂明显加快逆水煤气变换的反应速率,起到催化剂的作用,但是产生的CaS堵塞了脱硫剂的微孔,催化活性减弱,使逆水煤气变换反应速率减慢。