Selective CO Production Research Articles

Overturning CO2 Hydrogenation Selectivity from CH4 to CO by Strong Ru-FeOx Interaction Arising from a Multilayer Epitaxial Structure.

The catalytic conversion of CO2 to CO through hydrogenation has emerged as a promising strategy for CO2 utilization, given that CO serves as a valuable C1 platform compound for synthesizing liquid fuels and chemicals. However, the predominant formation of CH4 via deep hydrogenation over Ru-based catalysts poses challenges in achieving selective CO production. High reaction temperatures often lead to catalyst deactivation and changes in selectivity due to dynamic metal evolution or agglomeration, even with a classic strong metal-support interaction. Herein, we have developed a FeOx/Ru/Rutile multilayer epitaxial structure by depositing a FeOx layer onto the epitaxially grown RuO2 nanolayers on the surface of rutile nanoparticles. This multilayer epitaxial structure transformed into a structure in which Ru nanoparticles were decorated with FeOx layers with ultrastable strong metal-support interaction (SMSI). Subsequently, the FeOx decoration on Ru nanoparticles effectively shifted the dominant product from CH4 to 95% CO during CO2 hydrogenation. Remarkably, this catalyst exhibits exceptional stability and can be operated stably at 550 °C for a long time without apparent deactivation. Compared with the dynamic changes observed in supported Ru nanoparticles, the interaction between Ru and FeOx maintains their electronic states at different reaction temperatures. Furthermore, this Ru-FeOx interaction inhibits H2 activation capability, CO adsorption, and subsequent hydrogenation of CO. The transformation strategy employed here, which utilizes initial multilayer epitaxial structures, can be applied to construct SMSI to enhance metal catalysts' catalytic performance.

Fabrication of a Partial Encapsulation Architecture on S-Scheme Heterojunctions toward Durable Selective Photocatalytic CO2 Reduction.

It remains a challenging issue to achieve durably stable photocatalytic CO2 reduction over heterojunctions owing to their inherent structural assembly features. Herein, a unique partial encapsulation architecture is fabricated on the 3D/2D CoWO4/C3N5 heterojunction by embedding CoWO4 microspheres on C3N5 nanosheets, which achieves efficient, durable, stable, and selective photocatalytic CO2 reduction. For the optimal 5%-CoWO4/C3N5 heterojunction, the yield of selective CO2 reduction to CO is 7.70 and 3.82 times higher than those of CoWO4 and C3N5 in 4 h, respectively, and it maintains a stable CO generation rate within 20 cycles over 80 h. A series of characterization experiments and density functional theory calculations reveal that the structural stability is reinforced significantly via strong interfacial interaction owing to the unique partial encapsulation architecture fabricated on the 3D/2D CoWO4/C3N5 heterojunction, the separation efficiency of photogenerated carriers is improved by inducing a built-in electric field and triggering the S-scheme charge-transport path, and the high CO product selectivity is attributed to the much lower free energy required for the generation path of CO compared to that for CH4.

A local acidic environment at the copper/molten salt interface enabling the efficient CO2 to CO conversion

The electrochemical reactions highly rely on the chemical environments, however, this phenomenon remains poorly understood in nonaqueous electrolyte. Herein, we study the effect of the electrode chemical environments on the electrochemical reduction of CO2 in molten carbonate. Using a Cu foam electrode, an acidic (CO2-rich) environment is created to achieve the efficient direct reduction of CO2 rather than the indirect reduction of CO32–. The acidic environment promotes a selective CO production thermodynamically, achieving a high CO current efficiency of 99 % at a current density of 779–1039 mA cm−2 at 700 °C. The Cu foam electrode works stably over 100 h at 260 mA cm−2 with an overpotential of 304 mV. This work reveals the role of the local chemical environment at the electrode/molten salt interface in governing the product selectivity and energy consumption, which is helpful for designing efficient high-temperature CO2 electrolyzers.

Electrochemical Conversion of Bicarbonate Using Proton Exchange Membrane-Based Electrolyzer

Direct electrochemical conversion of captured carbon dioxide (CO2) is gaining interest as an efficient method for capturing and utilizing CO2, eliminating the need for energy-intensive CO2 separation process.[1] The integrated electrolyzer with bicarbonate feed operates on the principle of spontaneous reduction of CO2 released from bicarbonate within the electrolyzer. The key to the on-site decomposition of bicarbonate into CO2 is to acidify the bicarbonate within the electrolyzer through the deliberately generated pH gradient. Bipolar membrane has been extensively used to generate pH gradient and acidify the bicarbonate feed.[2] However, the high ionic resistivity of bipolar membrane and slow kinetic of water dissociation reaction can result in a high operation cell voltage.In this study, we demonstrate proton exchange membrane based-bicarbonate electrolyzer which produces carbon monoxide from bicarbonate feedstock with high CO production selectivity and low cell voltage that are comparable to the conventional gas fed CO2 electrolyzer. To achieve highly selective CO production selectivity, a nickel single atom catalyst (Ni SAC) where the atomically dispersed nickel active sites decorated on the nitrogen doped carbon was prepared and utilized. Ni-SAC showed high CO production selectivity even in bicarbonate feed electrolyzer. To further improve the performance of this integrated electrolyzer, significant attention was given to the optimization of electrode structures. Due to the complexity of the reaction environment within the integrated electrolzyer, the performance of the electrolyzer is heavily dependent on the porosity of electrodes and distribution of catalyst on the electrodes. By optimizing the fabrication of electrodes with Ni-SACs, the optimal catalyst coated electrode showed high CO production selectivity over 90% with current density of 100 mA/cm2 at low operating cell potential of 3 V.

Tailoring Cu-Based Electrocatalysts for Enhanced Electrochemical CO2 Reduction to Alcohols: Structure-Selectivity Relationship.

The use of CO2 as a feedstock for the production of carbon-based fuels and value-added chemicals offers a promising route toward carbon neutrality. In this study, two Cu-based electrocatalysts, namely, Cu24/N-C and Cu2/N-C, are successfully prepared by thermal treatment of Cu24 metal-organic polyhedron-loaded zeolitic imidazolate framework-8 (ZIF-8) nanocrystals (Cu24/ZIF-8) and Cu2 dinuclear compound-loaded ZIF-8 nanocrystals (Cu2/ZIF-8), respectively. Extensive structural and compositional analyses were conducted to confirm the formation of Cu nanocluster-loaded N-doped porous carbon supports in both Cu24/N-C and Cu2/N-C and Cu nanoparticles encapsulated by graphitic carbons in Cu2/N-C as well. These two Cu-based electrocatalysts exhibited different behaviors in the electrochemical CO2 reduction reaction (CO2RR). The Cu24/N-C electrocatalyst showed high selectivity for CO production, while Cu2/N-C showed a preference for alcohol generation. The excellent stability of Cu2/N-C over a 30 h continuous electrochemical reduction further highlights its potential for practical applications. The difference in electrocatalytic performance observed in the two catalysts for CO2RR was attributed to distinct catalytic sites associated with Cu nanoclusters and nanoparticles. This research reveals the significance of their structures and compositions for the development of highly selective electrocatalysts for CO2 reduction.

Structure Activity Relationships for Second‐Coordination Sphere Functional Group Dependent CO2 Reduction by Manganese Bipyridyl Electrocatalysts

AbstractA series of twelve second coordination sphere (SCS) functionalized manganese tricarbonyl bipyridyl complexes are investigated for their electrocatalytic CO2 reduction properties in acetonitrile. A qualitative and quantitative assessment of the SCS functional groups is discussed with respect to the catalysts’ thermodynamic and kinetic efficiencies, and their product selectivities. In probing a broad scope of functional groups, it is clear that only the aprotic ortho‐arylester SCS is capable of promoting the highly desired low‐overpotential proton‐transfer electron‐transfer (PT‐ET) pathway for selective CO production. The ortho‐phenolic analogues cause an increase in overpotential with a product selectivity favoring H2 evolution, consistent with a high‐overpotential pathway via the anionic [Mn−H]− intermediate. Alternative aprotic Lewis base functional groups such as trifluoromethyl, morpholine and acetamide are shown to also be capable of intermediate manganese hydride generation. The tertiary amine substituent, 2‐morpholinophenyl, exhibits a desirable product distribution characteristic of syn‐gas (CO : H2=30 : 48) with an impressive turnover frequency, while the secondary amine group, 2‐acetamidophenyl, induces a notable shift in selectivity with a faradaic yield of 55 % for the formate (HCO2−) product. In addition to their catalytic properties, cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC) studies are presented to probe pre‐catalyst electronic properties and the two‐electron reduction activation pathway.

Photocatalytic Optical Hollow Fiber with Enhanced Visible-light-driven CO2 Reduction.

A visible-light-driven CO2 reduction optical fiber is fabricated using graphene-like nitrogen-doped composites and hollow quartz optical fibers to achieve enhanced activity, selectivity, and light utilization for CO2 photoreduction. The composites are synthesized from a lead-based metal-organic framework (TMOF-10-NH2) and g-C3N4 nanosheet (CNNS) via electrostatic self-assembly. The TMOF-10-NH2/g-C3N4 (TMOF/CNNS) photocatalyst with an S-type heterojunction is coated on optical fiber. The TMOF/CNNS coating, which has a bandgap energy of 2.15eV, has good photoinduced capability at the coating interfaces, high photogenerated electron-hole pair yield, and high charge transfer rate. The conduction band potential of the TMOF/CNNS coating is more negative than that for CO2 reduction. Moreover, TMOF facilitates the CO desorption on its surface, thereby improving the selectivity for CO production. High CO2 photoreduction and selectivity for CO production is demonstrated by the TMOF/CNNS-coated optical fiber with the cladding/core diameter of 2000/1000µm, 10 wt% TMOF in CNNS, coating thickness of 25µm, initial CO2 concentration of 90 vol%, and relative humidity of 88% RH under the excitation wavelength of 380-780nm. Overall, the photocatalytic hollow optical fiber developed herein provides an effective and efficient approach for the enhancement of light utilization efficiency of photocatalysts and selective CO2 reduction.

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO2 Reduction.

Mechanistic studies involving characterization of crucial intermediates are desirable for rational optimization of molecular catalysts toward CO2 reduction, while fundamental challenges are associated with such studies. Herein we present the systematic mechanistic investigations on a pyrene-appended CoII macrocyclic catalyst in comparison with its pyrene-free prototype. The comparative results also verify the reasons of the higher catalytic activity of the pyrene-tethered catalyst in noble-metal-free CO2 photoreduction with various photosensitizers, where a remarkable apparent quantum yield of 36±3 % at 425 nm can be obtained for selective CO production. Electrochemical and spectroelectrochemical studies in conjunction with DFT calculations between the two catalysts have characterized the key CO-bound intermediates and revealed their different CO-binding behavior, demonstrating that the pyrene group endows the corresponding CoII catalyst a lower catalytic potential, a higher stability, and a greater ease in CO release, all of which contribute to its better performance.

Structural transformation of carbon-encapsulated core-shell CoNi nanoparticles during magnetically induced CO2 reduction into CO

Controlling product distribution in CO2 hydrogenation is of great scientific interest, the selective CO production through the reverse water-gas shift reaction (RWGS) being one of the most investigated processes. Herein, we report the synthesis of new core-shell Co@Ni NPs encapsulated in carbon (Co@Ni@C) to prevent their aggregation at the high-temperatures reached during magnetically induced catalysis. This bifunctional system has been simultaneously used as heating agent and catalyst for the magnetically induced hydrogenation of CO2. While at low magnetic fields Co@Ni@C produces CH4:CO mixtures, at higher field amplitudes it selectively generates carbon monoxide. Indeed, Co@Ni@C has shown to be one of the most active catalysts reported to date, which reaches a maximum conversion of 74.2% with complete selectivity towards CO at 53 mT and 300 kHz. In addition, recycling and cyclability experiments have demonstrated that Co@Ni@C becomes fully selective for CO after being exposed to high field amplitudes (i.e. reaction temperature above 500 °C), even when it exposed to low magnetic fields again. This change in the selectivity is due to an atomic rearrangement of the core-shell structure, as was confirmed by EDX, XAS, TPR and TPD analysis.

ALD-Engineered CuxO Overlayers Transform ZnO Nanorods for Selective Production of CO in Electrochemical CO2 Reduction.

The electrochemical CO2 reduction reaction (CO2RR) holds tremendous promise as a strategy for lowering atmospheric CO2 levels and creating new clean energy sources. The conversion of CO2RR to CO, in particular, has garnered significant scientific interest due to its industrial feasibility. Within this context, the CuZn-based electrocatalyst presents an attractive alternative to conventional CO-selective electrocatalysts, which are often costly and scarce. Nevertheless, the wide-range utilization of CuZn electrocatalysts requires a more comprehensive understanding of their performance and characteristics. In this study, we synthesized ZnO nanorods through electrodeposition and subsequently coated them with CuxO overlayers prepared by atomic layer deposition (ALD). CuxO significantly enhanced CO selectivity, and 88% CO selectivity at a relatively low potential of -0.8 V was obtained on an optimized CuxO overlayer thickness (CuxO-250/ZnO). The addition of CuxO on ZnO was found to dramatically increase the electrochemical surface area (ESCA), lower the charge-transfer resistance (Rct), and introduce new active sites in the ε-CuZn4 phase. Furthermore, electrochemical Raman spectroscopy results showed that the CuxO-250/ALD electrode developed a ZnO layer on the surface during the CO2RR, while the bare ZnO electrode showed no evidence of ZnO during the reaction. These results suggest that the addition of CuxO by ALD played a crucial role in stabilizing ZnO on the surface. The initial amount of CuxO was shown to further affect the redeposition of the ZnO layer and hence affect the final composition of the surface. We attribute the improvement in CO selectivity to the introduction of both ε-CuZn4 and ZnO that developed during the CO2RR. Overall, our study provides new insights into the dynamic behavior and surface composition of CuZn electrocatalysts during CO2RR.

A membrane electrode assembly-type cell designed for selective CO production from bicarbonate electrolyte and air containing CO2 mixed gas

A membrane electrode assembly-type electrochemical cell consisting of an all-Ag flow channel exhibits selective CO production from bicarbonate electrolyte and air containing CO2 mixed gas.

Improved electrochemical reduction of CO2 to syngas with a highly exfoliated Ti3C2Tx MXene-gold composite.

Transforming carbon dioxide (CO2) into valuable chemicals via electroreduction presents a sustainable and viable approach to mitigating excess CO2 in the atmosphere. This report provides fresh insights into the design of a new titanium-based MXene composite as a catalyst for the efficient conversion of CO2 in a safe aqueous medium. Despite its excellent electrocatalytic activity towards CO2 reduction and high selectivity for CO production, the high cost of Au and the decline in catalytic activity on a larger scale hinder its large-scale CO2 conversion applications. In this research, we have successfully prepared an Au/Ti3C2Tx composite and tested its catalytic activity in the electrochemical CO2 reduction reaction (ECRR). The as-prepared composite features strong interactions between gold atoms and the MXene support, achieved through the formation of metal-oxygen/carbon bonds. The Au/Ti3C2Tx electrode demonstrated a significant current density of 17.3 mA cm-2 at a potential of -0.42 V vs. RHE, in a CO2 saturated atmosphere (faradaic efficiency: CO = 48.3% and H2 = 25.6%). Nyquist plots further indicated a reduction in the charge-transfer resistance of the Au/Ti3C2Tx layer, signifying rapid charge transfer between the Au and Ti3C2Tx. Furthermore, it is known that liquid crossover through the Gas Diffusion Electrode (GDE) significantly improves CO2 diffusion to catalyst active sites, thereby enhancing CO2 conversion efficiency. The goal of this work is to design an interface between metal and MXene so that CO2 can be electroreduced to fuels and other useful chemical compounds with great selectivity.

Controlled synthesis of silver/silicon hybrid nanostructures enables enhanced photocatalytic CO2 reduction.

Localized surface plasmon resonances in plasmonic nanoparticles enable effective photon harvesting and generate energetic electrons and holes. However, fast charge recombination and surface contamination due to reactant-involved synthesis can significantly hinder the activity. Herein, we report a facile, solution-processed synthesis of hybrid uncoated silver nanoparticles combined with silicon nanocrystals to address these issues. The resulting hybrid nanocolloid exhibits enhanced photocatalytic CO2 reduction, achieving 1552 μmol g-1 and 100% selectivity for CO production.

Selective CO production from CO2 over a metal catalyst supported on perovskite oxide in the presence of excess hydrogen

Supporting platinum on perovskite-type oxides (BZY10) increased catalytic activity while maintaining in the reverse water–gas shift reaction, which reduces carbon dioxide to carbon monoxide.

Selective CO production via a dual-defective CdS/BiOCl photocatalyst for CO2 photoreduction

An S-scheme heterostructure can effectively improve the separation of photogenerated carriers. Dual-defective introduction can not only stabilize the *COOH intermediates, but also greatly reduce the energy barrier from releasing the final product CO.

High N-containing porphyrinic C3N4 hybrid polymeric material as efficient photocatalyst for selective CO2 reduction

A new porphyrinic-C3N4 material was successfully synthesized using a new method and was characterized at each stage of the process using a range of spectroscopic techniques, including FT-IR and NMR. The XPS, SEM, and EDX studies of the material were also carried out which showed only one dominant morphology and the existence of C and N in the compound which confirm the formation of Por-C3N4. The material was loaded with Co2+ ions by mixing and stirring methanolic solution of Co(O2CH3).4H2O with DMF solution of por-C3N4 for 24 h and the resulting dried compound was subjected to carbonization. The PXRD pattern proved that Co-por-C3N4 did not degrade into oxide, hydroxide, or any other form of Co. The photocatalyst exhibited a higher selectivity for CO production of 11 μmol g−1 (at pH = 11) compared to 6.7 μmol g−1 (at pH = 8) from CO2. The result indicates the possibility of integrating the porphyrin component into C3N4 units via covalent attachment to create a 3D hybrid polymer which was described in the result and discussion section. This polymer shows promise in efficiently transforming CO2 into CO under visible light exposure, offering promising prospects for solar-driven CO production from CO2.

Large-scale CO2-to-CO electroconversion on highly efficient diatomic catalysts

For commercialization of electrochemical CO2 reduction reaction, it is of great significance to achieve highly efficient and large-scale electrolysis at an industrially meaningful scale. Herein, for the first time, a highly efficient diatomic catalyst with neighboring Ni-N4 and oversaturated Fe-N5 moieties is successfully prepared via a scalable strategy for industrial-current CO2 electrolysis in large-scale electrolyzer. In zero-gap membrane electrode assembly (MEA) cell with active area of 25 cm2, the resulting diatomic catalyst delivers a near-unity selectivity toward CO production at an industrially relevant current density of 200 mA cm−2. By further scaling up the electrode into active area of 140 cm2, this catalyst maintains a high-current electrolysis at 28 A with an impressive CO selectivity of > 97 % and single-pass CO2 conversion can reach ∼32 % even at a high CO2 flow rate of 600 mL min-1. Most importantly, an exclusive CO production rate of ∼45 L h-1 can be achieved by assembling four single cells sized of 140 cm2 in an electrolyzer stack. The detailed experimental measurements and theoretical calculations reveal that synergistic electronic modulation effect of dual-atomic sites strengthens the capability to favor the selective CO production. Our findings should pave the way for ultimate application of a high-performance diatomic catalyst to industrial implementation of CO2 electroreduction.

Rb-Ni/Al2O3 as dual functional material for continuous CO2 capture and selective hydrogenation to CO

Ni-based dual-functional materials (DFMs) have been widely investigated for CO2 capture and reduction with H2 (CCR). However, controlling the selectivity of CO2 hydrogenation to CH4 or CO is a fundamental challenge. Most Ni-based DFMs favor the selectivity of CH4 over CO, although CO is more desirable than CH4 from a chemical-synthesis perspective. In this study, Rb-promoted Ni nanoparticles on Al2O3, Rb-Ni/Al2O3, are developed as an effective DFM for selective CO production through CCR with a CO2 conversion of 68% and a CO selectivity of 97% under isothermal conditions at 450 °C in the mixture of O2 during CO2 capture process. The developed Rb-Ni/Al2O3 is applicable to continuous CCR using double reactor system. The roles of Rb and Ni in CCR over Rb-Ni/Al2O3 for CO formation are also discussed based on temperature-programmed surface reactions and in situ spectroscopic studies.

Atomic Zn-Doping Induced Sabatier Optimum in NiZn0.03 Catalyst for CO2 Electroreduction at Industrial-Level Current Densities.

The Sabatier principle defines the essential criteria for an ideal catalyst in heterogeneous catalysis, while reaching the Sabatier optimum is still challenging in catalyst design. Herein, an elegant strategy is described to reach the Sabatier optimum of Ni electrocatalyst in CO2 reduction reaction (CO2 RR) by atomically Zn doping. The incorporation of 3%Zn single atom into Ni lattice leads to the moderate degrade of d-band center via Ni-Zn electronic coupling, which balances the bonding strengths of *COOH and *CO, resulting in a relative low energy barrier for CO2 activation while not being substantially poisoned by CO. Consequently, NiZn0.03 /C exhibits unique catalytic activity (jCO >100mAcm-2 at -0.6V), wide potential range for selective CO production (FECO >90% from -0.65 to -1.15V), and outstanding long-term stability (FECO >90% during 85h electrolysis at -0.85V). The results provide valuable insights for the rational fabrication of superior non-noble bimetallic electrocatalysts in CO2 electroreduction.

Integrated capture and solar-driven utilization of CO2 from flue gas and air

Integrated capture and solar-driven utilization of CO2 from flue gas and air