H2-rich Stream Research Articles

Poisoning effect of chlorine anions in the catalytic activity of CuO/CeO2/UiO-66 for CO-PROX reaction and strategy for catalyst activation.

UiO-66 was synthesized using ZrOCl2·8H2O as metal precursor, and CuO/CeO2/UiO-66 catalysts were prepared and tested for preferential CO oxidation in H2-rich streams (CO-PROX reaction), a reaction of practical significance in hydrogen purification for fuel cells. The study highlights the detrimental effect of residual chlorine anions from UiO-66 synthesis and DMF washing on the catalytic performance of CuO/CeO2/UiO-66. An activation strategy involving rigorous water washing and thermal treatment at 160 ºC under CO-PROX conditions was developed. Both steps were deemed necessary, as employing only one proved insufficient to reduce chlorine levels to non-poisoning thresholds. This activation procedure does compromise UiO-66 crystallinity and porosity, but it is justified by achieving a fully functional catalyst. TEM images confirm the uniform dispersion of the CuO/CeO2 active phase on the UiO-66 matrix post-activation and after catalytic testing. A 16-hour CO-PROX test at 160 ºC with the CuO/CeO2/UiO-66 catalyst, once activated, demonstrated stable performance throughout the extended long-term experiment. This research provides valuable insights into optimizing CuO/CeO2/UiO-66 catalysts for CO-PROX application.

Highly stable platinum catalyst encapsulated with mesoporous silica for preferential oxidation of CO in H2-rich stream

Preferential oxidation of CO in H₂-rich streams (PROX) is an effective method to reduce trace amounts of CO for proton exchange membrane fuel cells. However, developing highly stable catalysts for practical reaction conditions achieving the 50:50 goal—below 50 ppm CO concentration with 50% O₂ selectivity—remains challenging. Here, we report a highly stable Pt nanoparticle catalyst encapsulated in mesoporous silica (Pt@mSiO2) loaded on a monolith, which achieves the 50:50 goal. Over 1000 h of continuous PROX reactions in the presence of H2O and CO2, the catalyst maintained an average CO concentration of ca. 33 ppm and O2 selectivity of ca. 50%. The excellent activity, selectivity, and long-term stability of Pt@mSiO₂, which can be attributed to the small size (ca. 2.7 nm) of Pt nanoparticles stably encapsulated in interconnected micro- and meso-porous silica without agglomeration, offer great potential for practical PROX applications.

Novel Ni–Ru/CeO2 catalysts for low-temperature steam reforming of methane

Upgrading of biogas and biomethane into H2-rich streams by steam reforming is regarded as an effective strategy to reduce fossil fuel consumption contributing to the transition towards a green energy system. In this context, novel reactor configurations such as membrane reactors appear a promising route for process intensification, but they require novel catalysts more active at low temperatures, stable, and resistant to coke formation. In this work, we prepared and tested structured catalysts characterized by a low Ni content (7 wt%) and a very low Ru content (≤1 wt%) supported on ceria and deposed onto SiC monoliths. Catalysts were tested at low temperatures (<600 °C), i.e. at temperatures suitable for applications in Pd-based membrane reactors. Fresh and used catalysts were characterized by ICP-MS, N2 physisorption, XRD, TEM, SEM-EDS, XPS and H2-TPR to identify the physicochemical properties affecting the catalytic activity. The catalysts showed good activity towards methane reforming, stable performance, and good resistance to coke formation. Ruthenium affects both the intrinsic catalytic activity and the resistance to the inhibiting effect of steam on the reaction rate. This is related to improved redox properties due to the intimacy between the active metals and their strong-metal-support-interaction with the ceria. Finally, our catalysts show self-activation under reaction conditions, which is an interesting property for applications.

A combined experimental and simulations assessment of CO2 capture and CO2/H2 separation performance of aminosilane-grafted MCM-41 and pore-expanded MCM-41

Amine-functionalized mesoporous silica materials have attracted considerable attention as robust adsorbents for large-scale CO2 capture and direct air capture (DAC). Amine grafting increases selective affinity at low pressures, yet also often reduces the adsorbent's pore volume and surface area, affecting the kinetics and capacity upon CO2 adsorption. MCM-41 and pore-expanded MCM-41 (PE-MCM-41) were developed here, functionalized using 3-aminopropyl triethoxy silane (APTES), and comparably evaluated for their carbon capture performance at different conditions by a combinational experimental, equilibrium and kinetic modelling, and molecular simulations approach. In specific, CO2 adsorption capacity, CO2/N2 selectivity, CO2 adsorption at humid conditions, heat of adsorption, and regeneration/cyclability were assessed, coupled to molecular simulation insights on the physisorption and chemisorption contribution to the overall adsorption uptake. Indicatively, a capacity value of 3.07 and 2.44 mmol/g was obtained for APTES-PE-MCM-41, and 2.27 and 1.89 mmol/g for APTES-MCM-41, under wet and dry conditions, respectively. The CO2 selective adsorption from H2 rich gas streams was also examined over APTES-MCM-41 in order to assess the potential application in H2 stream purification process. The latter is of high significance in order to use hydrogen as fuel e.g. in anion exchange membrane fuel cells for power production since the presence of CO2 in the feed composition is considered a major drawback in their commercialization.

Effect of Copper Particle Size on the Surface Structure and Catalytic Activity of Cu–CeO2 Nanocomposites Prepared by Mechanochemical Synthesis in the Preferential CO Oxidation in a H2-Rich Stream (CO-PROX)

An effect of Cu powder dispersion and morphology on the surface structure and the physical–chemical and catalytic properties of Cu–CeO2 catalysts prepared by mechanochemical synthesis was studied in the preferential CO oxidation in a H2-rich stream (CO-PROX). Two catalysts, produced by 30 min ball-milling from CeO2 and 8 mass% of copper powders and with particle sizes of several tens (dendrite-like Cu) and 50–200 nm (spherical Cu obtained with levitation-jet method), respectively, were characterized by X-ray diffraction and electron microscopy methods, a temperature-programmed reduction with CO and H2, and with Fourier-transform infrared spectroscopy. The catalyst synthesized from the “large-scale” dendrite-like Cu powder, whose surface consisted of CuxO (Cu+) agglomerates located directly on the surface of facetted CeO2 crystals with a CeO2(111) and CeO2(100) crystal planes exposition, was approximately two times less active at 120–160 °C than the catalyst synthesized from the fine Cu powder, whose surface consisted of CuxO (Cu2+) clusters of 4–6 nm in size located on the steps of facetted CeO2 nanocrystals. Although a large part of CO2 reacted with a ceria surface to give carbonate-like species, no blockage of CO-activating centers was observed due to the surface architecture. The surface structure formed by the use of highly dispersed Cu powder is found to be a key factor responsible for the catalytic activity.

Initial Research on the 1%CuO – 6CeO2 – 4ZrO2 Catalysts by TPR-H2 for the Carbon Monoxide Preferential Oxidation (CO-PROX Reaction)

The 1wt%CuO – 6CeO2 – 4ZrO2 catalysts were synthesized by sol-gel method with two different procedures: (i) impregnating CuO on CeO2-ZrO2 support (CuO/CeO2-ZrO2), (ii) sol-gel of the Cu, Ce and Zr precursor together (CuO-CeO2-ZrO2). These catalysts were applied for the preferential oxidation of carbon monoxide (CO-PROX) to remove a small quantity of CO in an H2-rich stream (the new research direction in Viet Nam), fueling the proton exchange membrane fuel cell (PEMFC) energy system. The findings of the TPR-H2 experiment indicated that the catalyst produced through the first method exhibited an α reduction peak at 174 °C, which shows the effective dispersion of copper species. In combination with EPR results, the author anticipates a significant dispersion arising from isolated copper, which is recognized as a pivotal site in the CO-PROX reaction per numerous reputable studies. The catalyst synthesized by the second method did not provide a clear indication of the oxidation behavior of Cu-species. Therefore, it can be inferred that this catalyst is inappropriate for the low-temperature CO-PROX reaction.

Bi-doped CuCeO2−x nanorod catalysts for photothermal CO-PROX in H2-rich streams: Enhanced oxygen vacancy and light absorption capacity

The wide band gap of ceria limited the light absorption and photothermal conversion of copper-ceria catalyst for photothermal preferential oxidation of CO (CO-PROX). In the present work, doping Bi element was adopted to regulate the energy band and catalytic performance of CuCeO2−x nanorod catalysts for photothermal CO-PROX. Bi/CuCeO2−x nanorods were synthesized by co-precipitation hydrothermal and deposition precipitation method. The Bi/CuCeO2−x catalyst with the molar ratio of Bi/Ce 2.5% exhibited the best catalytic performance and the CO conversion reached 90% under 2.5 suns with a surface temperature of 120 °C. The doped Bi species were incorporated into the CeO2 lattice and promoted the formation of oxygen vacancy sites and the strong Cu-Ce interaction, as revealed by XRD, XPS, Raman and H2-TPR results. In addition, doping Bi reduced the band gap of ceria nanorod from 2.77 to 2.47 eV and remarkably enhanced the UV–vis light response and photogenerated carrier separation of Bi/CuCeO2−x-2.5.

Gold supported on Gd-doped CeO2 nanorods applied as water-gas shift catalyst under H2 rich stream

In this work, we report the synthesis of catalysts based on ceria nanorods (CeO2NRs) doped with 3% and 5% mol gadolinium. The supports were obtained from cation co-precipitation hydrothermal synthesis over which gold nanoparticles (AuNPs) were deposited by the deposition-precipitation (DP) methodology, allowing the Au nanoparticles size control at around 3 nm. The catalysts were evaluated in water gas shift reaction and showed high activity under a H2 rich stream (7%CO/7%CO2/14%N2/42%H2/30%H2O) with steam/process gas molar ratio (S/G) of 0.3 at 300 and 250 °C. The results revealed that Gd-doping increased the oxygen vacancies concentration due to the insertion of a trivalent cation in ceria lattice. In addition, the synergistic effect between AuNPs and Gd-doped CeO2 provided the increase of reducibility and oxygen storage capacity (OSC). These properties were associated with the catalytic activity in water gas shift reaction. The nanostructured materials decreased the CO concentration under conditions of H2 rich stream, indicating the catalysts potential for industrial applications after further studies. The catalyst doped with 5% mol Gd was the most active and achieved 24% of CO conversion at 300 °C.

Oxygen vacancy-regulated atomic dispersed Au on CeFeOx for preferential oxidation of CO in H2-rich stream

CO preferential oxidation in H2-rich stream (CO-PROX) is a critical reaction for H2 purification in emerging hydrogen economy including advanced fuel cell technology. Au-based catalysts are viewed as some of the most promising catalysts but achieving high catalytic efficiency and selectivity is still challenging. Defect engineering is deemed as a powerful strategy to improve the intrinsic catalytic activity. Herein, CeFeOx-supported Au catalysts with controllable oxygen vacancy (Ov) concentrations were obtained and applied to CO-PROX. The results of characterizations showed that the Ovs were preferentially generated in conjunction with Au single atoms (SAs) rather than nanoparticles (NPs), which further modulated the surface electronic properties via surplus electrons in Ovs and enhanced the interfical interaction between Ovs and Au SAs. The CO-PROX results indicated that the reduced Au SA catalyst (Au1/CeFeOx-R) with the highest Ov concentration completely converted CO at temperature of 80 °C with relatively low reactivity towards H2 oxidation. The remarkable catalytic activity and selectivity were attributed to the modified electronic properties by Ovs that played a bridging role in electron transfer and accelerated reaction process, as well as the coupling effect of Ovs and Au SAs that enhanced the dissociative adsorption of O2 and the adsorption-oxidation of CO, resulting in a reduced reaction energy barrier and making CO oxidation more favorable than H2 oxidation. This research opens up an alternative strategy to simultaneously stabilize and activate single-atom catalysts.

Synergistic effect of platinum single atoms and nanoclusters for preferential oxidation of carbon monoxide in hydrogen-rich stream

Despite the maximum atom-utilization efficiency and remarkable activity of single-atom catalysts, further improvement of catalytic activity can be obtained by the synergistic effect of single atoms and nanoclusters in some catalytic systems. Herein, CeFeOx-supported Pt single atoms coupling with subnanometric clusters (Pt1-Ptn) structures are developed via a facile strategy. They are applied as the highly efficient catalysts for the preferential oxidation of CO in H2-rich stream (CO-PROX), which achieve complete elimination of CO at low temperature of 50 °C, with a wide operating temperature window and extraordinary stability for over 500 h without noticeable deactivation. The exceptional performance is attributed to the synergistic effect of distinctive Pt1-Ptn structures, which couple the benefits of Pt single atoms and subnanometric clusters in a remarkable way. The disadvantages of single Pt species catalysts, such as sensibility to strong adsorption of CO or reduced lattice oxygen reactivity due to excessive coordination, can be well mitigated. The results of detailed characterizations and density functional theory calculations confirm that the unique structures possess moderate adsorption strength for CO and create abundant active interfacial oxygen species, because of the absence of bulk metallic Pt0 and appropriate coordination to lattice oxygen, which synergistically facilitate the catalytic performance.

Chemical looping preferential oxidation of CO over ceria-supported γ-Fe2O3

A novel chemical looping preferential oxidation (CL-PROX) process is proposed and demonstrated for eliminating trace CO from a H2-rich stream. The proposed process exhibited an excellent CO removal performance (CO concentration < 100 ppm) and a high H2 recovery (>∼96 %) with a ceria-supported γ-Fe2O3 oxygen carrier. It was obtained by activating the fresh sample that was synthesized through a co-precipitation method and the innovative activation process comprising a partial reduction step at 400 °C followed by an oxidation process at 260 °C. The structure and evolution of iron species in the oxygen carrier were investigated through experimental characterizations during activation and redox cycles. TPR characterizations illustrated a significant difference in the reducibility of the active species, γ-Fe2O3, under H2 and CO atmospheres, which could be the evidence for its relatively high selectivity to CO oxidation. In-situ FTIR characterization also pointed out that the desorption of reaction intermediates to CO2 is facilitated via the reduction of the surface γ-Fe2O3, which might contribute to the outstanding CO oxidation performance of the oxygen carrier. The successful application of chemical looping process to selective oxidation of CO in H2-rich gas not only illustrates a new strategy for H2 purification, but also provides insights into the redox reaction mechanism with the newly-prepared γ-Fe2O3-based oxygen carrier.

An efficient Sn-modified Pd-Cu/Al2O3 catalyst for H2 purification through preferential oxidation of CO at low temperature

A series of Pd-Cu-xSn/Al2O3 catalysts with the low tin content (Sn/Cu atomic ratio = 0.1, 0.25, 0.5) is obtained by the facile impregnation routes and employed for low-temperature CO preferential oxidation (CO-PROX) in H2-rich stream. The catalytic performance tests show that the suitable addition of Sn possesses the positive effects on Pd-Cu/Al2O3 for CO-PROX, that is, PC-0.25Sn-Al (Sn/Cu atomic ratio = 0.25) exhibits better catalytic activity and stability at 30 °C. The systematic characterization results demonstrate the moderate incorporation of SnCl4 to Pd-Cu/Al2O3 drives the generation of SnO2, which promotes the strong interaction between Sn species and Pd-Cu/Al2O3. And it is conductive to improving the structure stability of active Cu2Cl(OH)3 species and the better water resistance of PC-0.25Sn-Al. Furthermore, the doping of Sn in PC-0.25Sn-Al may retard the reduction of active Pd species, promoting the absorption/activation and oxidation of CO on active Pd species. Meanwhile, the appropriate amount of Sn in PC-0.25Sn-Al readily provides more electron-rich active Cu+ species in the reaction stream, which is favorable to the reoxidation of Cu+ species by O2/active oxygen to Cu2+ species. These will favour the durative catalytic recycle of Pd and Cu species in PC-0.25Sn-Al and the enhancement of its catalytic activity and stability.

Three birds, one-stone strategy for synthesis of hierarchically arrayed defective MnCo2O4@NF catalyst for photothermal preferential oxidation of CO in H2-rich streams

A novel strategy with the “three birds, one stone” effect has been proposed to enhance the catalytic performance of cobalt manganese spinel catalysts for photothermal CO-PROX in H2 streams. The approach involves fabricating hierarchically arrayed defective MnCo2O4@ Nickel foam (NF) through a simple hydrothermal post-treatment and partial recrystallization process. Three synergetic effects were induced by the hydrothermal posttreatment of MnCo2O4: (i) the creation of a hierarchically arrayed morphology that strengthens light absorption and photo-to-thermal conversion, supported by finite-element method (FEM) simulations; (ii) the increased vacancy structures to alleviate significant electron-hole recombination; and (iii) abundant oxygen vacancy to facilitate oxygen adsorption and activation. These effects result in the unique hierarchically arrayed morphology and superior structural properties of MnCo2O4 spinel, which significantly enhances the photothermal synergism and catalytic activity of MnCo2O4@NF in photothermal CO-PROX driven by simulated solar light. This work provides a simple and facile strategy for developing hierarchical and defective MnCo2O4 spinel photothermal materials.

Effect of acid treatment on the catalytic performance of CuO/Cryptomelane catalyst for CO preferential oxidation in H2-rich streams

The effect of acid treatment on the catalytic performance of CuO/Cryptomelane (CuO/CR) for CO preferential oxidation (CO-PROX) in H2-rich streams has been investigated. The CR supports are synthesized via the sol-gel approach. The hydrochloric acid or water is used to treat the CR support, and the corresponding CuO/CR catalysts are prepared by an initial wet impregnation method. Compared with the pristine CuO/CR and water-treated CuO/CRW catalysts, the acid-treated CuO/CRH exhibits the best catalytic activity with almost 100% of CO conversion at 110 °C, which can be maintained at least 100 h. The characterization results show that acid treatment decreases the K+ content in the CuO/CRH catalyst, which is conducive to the formation of more oxygen vacancies, thereby promoting the reducibility of CuO/CRH. This is the main reason for the high catalytic activity of the acid-treated CuO/CRH catalyst. Moreover, the abundant Brönsted acid sites on CuO/CRH are favorable for the desorption of acidic product CO2, which also could result in the significant promotion of the catalytic activity for CO-PROX. This study sheds a light on the importance of acid treatment for cryptomelane and provides an efficient catalyst for hydrogen purification.

CO preferential oxidation in H2-rich stream over the CuO-MnOx mixed oxide catalysts prepared by a facile mechanochemical preparation method

The CuMn samples with various CuO weight percentages were synthesized by the mechanochemical route. The catalytic activity of the prepared samples was determined in the preferential oxidation of CO process (CO-PROX) in the temperature range of 40–250 °C. According to the XRD results, the 5CuMn and 10CuMn samples exhibited the spinel phase in their structures. The spinel phase formation enhanced the CO adsorption active sites and modified the redox properties. The results indicated that the copper incorporation into the manganese oxide modified the catalytic activity and structural properties. The 5CuMn catalyst with the highest BET area (72.1 m2 g−1) possessed 96% CO conversion and 50% CO2 selectivity at 70 °C (GHSV = 30,000 ml/h.gcat) and significant resistance in the presence of water due to the formation of hydroxyl groups over the catalyst surface. The catalyst activity remained stable for 14 h at 130 °C. Furthermore, the influence of calcination temperature, feed composition, and GHSV value on the catalytic performance of the 5CuMn catalyst was studied.

Microwave non-thermal fusion of MOFs derived Cu-O-Ce interface for boosting CO preferential oxidation

Engineering of uniformly-distributed and well-combined multi-component interface is sustainable but challenging for acquiring heterogeneous catalysts. Herein, the low energy consumption of microwave-fuse preparation is imposed on metal-organic frameworks (MOFs) namely Cu-MOF and Ce-MOF to manipulate Cu-O-Ce interface for preferential CO oxidation in H2-rich stream. By comprehensive characterizations, it is discovered that a unique spontaneous-migration of active Cu species onto Ce matrix will be driven by the microwave-fuse to form evenly-distributed and compactly-integrated Cu-O-Ce interface at low temperature, which is 200 °C lower than that required by traditional pyrolysis, clearly indicating the unique non-thermal function of microwave processing on fine-tuning oxide composite interface. In-situ Raman and in-situ DRIFTs further elucidate the improvement on synergistic redox feature along Cu2+-Ovac-Ce3+, leading to 100 % conversion of CO at 75–170 °C. These findings suggest that the unique self-migration of active metal species driven by non-thermal microwave-fuse is worthy of noting as an applicable strategy to acquire efficient multi-component solid interface for advanced heterogeneous catalysis as well as the current system for preferential CO oxidation in H2.

Novel process design and techno-economic simulation of methanol synthesis from blast furnace gas in an integrated steelworks CCUS system

A novel process design and techno-economic performance assessment for methanol synthesis from Blast Furnace Gas (BFG) is presented. Methanol synthesis using BFG as a feedstock, based on direct CO2 hydrogenation at commercial scale was simulated using Aspen Plus software to evaluate its technical performance and economic viability. The applied process steps involve first conditioning BFG using adsorption based desulfurisation, water-gas shift, dehydration, then separation of components into N2, CO2 and H2 rich streams using pressure swing adsorption. The H2 stream and a fraction of the CO2 stream are fed to a methanol synthesis system, while the remaining CO2 may be considered for geological storage in a Carbon Capture, Utilization and Storage (CCUS) case, or not in a Carbon Capture Utilization (CCU) case. Techno-economic analysis confirms methanol production from BFG is economically attractive under certain conditions, with Levelized Cost of Methanol production (LCOMeOH) calculated to be 344.61 £/tonne-methanol, and costs of CO2 avoided of − 20.08 £/tonne-CO2 for the CCU process and 9.01 £/tonne-CO2 for the CCUS process when using a set of baseline engineering assumptions. Sensitivity analysis of the process simulation explores opportunities for optimising the methanol synthesis system in terms of the impact of reactor size and/or recycle ratio on LCOMeOH. Economic viability of the CCU(S) processes is also found to be highly dependent on the cost of the feedstock BFG. Future cost savings as compared to business-as-usual steel production by 2030 in consideration of expected increases in the carbon price are estimated to be 10.59 £/tonne-steel for CCU and 24.61 £/tonne-steel for CCUS.

A novel process of cyclic adsorption and plasma-desorption for ppm-level CO removal from H2-rich stream

A cyclic adsorption and plasma-desorption (CAPD) process is applied to remove ppm-level carbon monoxide (CO) from the H2-rich stream for the first time. In the CAPD process, CO is first selectively adsorbed on CuCl/γ-Al2O3 till adsorption saturation; Then, the adsorbed CO is in-situ desorbed by plasma generated in dielectric barrier discharge (DBD) and the adsorbent is regenerated simultaneously. The effects of discharge power (Pdis) and flow rate of discharge gas (FD) on performances of plasma-desorption are investigated. The time to reach desorption of 50% (t50) and 90% (t90) significantly decreases with Pdis but is weakly correlated to the FD. At the investigated conditions, t50 and t90 are lower than 2.6 min and 4.5 min, respectively, which indicates that plasma-desorption features high desorption rate. In addition, desorption efficiency of plasma-desorption is higher than 98%. Moreover, CAPD process stability is preliminarily confirmed by six consecutive adsorption-desorption cycles.

Lab-scale experimental demonstration of Ca[sbnd]Cu chemical looping for hydrogen production and in-situ CO2 capture from a steel-mill

In the present work, a lab-scale packed bed reactor has been used to decarbonize mixtures of inlet gases simulating the typical composition of blast furnace gases (BFG) and convert them to H2-rich streams by means of the CaCu chemical looping concept. The reactor was packed with 355 g of Cu-based oxygen carrier (OC) supported on Al2O3 and natural Ca-based sorbent. The three main reaction stages; namely (i) Calcium Assisted Steel-mill Off-gas Hydrogen (CASOH), (ii) Cu oxidation and (iii) Regeneration of carbonated Ca-based sorbent were examined. In CASOH stage, BFG is converted into H2-rich stream (17% by vol.) under the experimental conditions of 600 °C, 5.0 bar and S/CO molar ratio of 2.0. A controlled oxidation causes a mere 3.5% of CaCO3 to decompose during the Cu-oxidation stage. This resulted in a nearly pure N2 stream at 600 °C and 5.0 bar operating conditions. During the regeneration stage, BFG and mixture of BFG and CH4 is used as a reducing fuel. To ensure the amount of heat needed for the decomposition of CaCO3 during the reduction of CuO, a 1.4 CuO/CaCO3 molar ratio has been used. It resulted in 46% CO2 in N2 at the end of the reduction/calcination stage.

Effect of noble metal addition over active Ru/TiO2 catalyst for CO selective methanation from H2 rich-streams

Selective CO methanation from H2-rich stream has been regarded as a promising route for deep removal of low CO concentration and catalytic hydrogen purification processes. This work is focused on the development of more efficient catalysts applied in practical conditions. For this purpose, we prepared a series of catalysts based on Ru supported over titania and promoted with small amounts of Rh and Pt. Characterization details revealed that Rh and Pt modify the electronic properties of Ru. The results of catalytic activity showed that Pt has a negative effect since it promotes the reverse water gas shift reaction decreasing the selectivity of methanation but Rh increases remarkably the activity and selectivity of CO methanation. The obtained results suggest that RuRh-based catalyst could become important for the treatment of industrial-volume streams.