Improving Stability of CO2 Electroreduction by Incorporating Ag NPs in N-Doped Ordered Mesoporous Carbon Structures.

The electroreduction of carbon dioxide (eCO2RR) to CO using Ag nanoparticles as an electrocatalyst is promising as an industrial carbon capture and utilization (CCU) technique to mitigate CO2 emissions. Nevertheless, the long-term stability of these Ag nanoparticles has been insufficient despite initial high Faradaic efficiencies and/or partial current densities. To improve the stability, we evaluated an up-scalable and easily tunable synthesis route to deposit low-weight percentages of Ag nanoparticles (NPs) on and into the framework of a nitrogen-doped ordered mesoporous carbon (NOMC) structure. By exploiting this so-called nanoparticle confinement strategy, the nanoparticle mobility under operation is strongly reduced. As a result, particle detachment and agglomeration, two of the most pronounced electrocatalytic degradation mechanisms, are (partially) blocked and catalyst durability is improved. Several synthesis parameters, such as the anchoring agent, the weight percentage of Ag NPs, and the type of carbonaceous support material, were modified in a controlled manner to evaluate their respective impact on the overall electrochemical performance, with a strong emphasis on operational stability. The resulting powders were evaluated through electrochemical and physicochemical characterization methods, including X-ray diffraction (XRD), N2-physisorption, Inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy (SEM), SEM-energy-dispersive X-ray spectroscopy (SEM-EDS), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), STEM-EDS, electron tomography, and X-ray photoelectron spectroscopy (XPS). The optimized Ag/soft-NOMC catalysts showed both a promising selectivity (∼80%) and stability compared with commercial Ag NPs while decreasing the loading of the transition metal by more than 50%. The stability of both the 5 and 10 wt % Ag/soft-NOMC catalysts showed considerable improvements by anchoring the Ag NPs on and into a NOMC framework, resulting in a 267% improvement in CO selectivity after 72 h (despite initial losses) compared to commercial Ag NPs. These results demonstrate the promising strategy of anchoring Ag NPs to improve the CO selectivity during prolonged experiments due to the reduced mobility of the Ag NPs and thus enhanced stability.

[1]  Sizhuo Chen,et al.  A Highly Dispersed and Surface-Active Ag-Btc Catalyst with State-of-The-Art Selectivity in Co2 Electroreduction Towards Co , 2023, SSRN Electronic Journal.

[2]  Guangxing Yang,et al.  Effects of nitrogen and oxygen on electrochemical reduction of CO2 in nitrogen-doped carbon black , 2023, Carbon.

[3]  Kuan-Chi Wu,et al.  Porous Zn Conformal Coating on Dendritic‐Like Ag with Enhanced Selectivity and Stability for CO2 Electroreduction to CO , 2022, Advanced Sustainable Systems.

[4]  A. Forner‐Cuenca,et al.  When Flooding Is Not Catastrophic—Woven Gas Diffusion Electrodes Enable Stable CO2 Electrolysis , 2022, ACS applied energy materials.

[5]  Yanfang Song,et al.  Chloride Ion Adsorption Enables Ampere-Level CO2 Electroreduction over Silver Hollow Fiber. , 2022, Angewandte Chemie.

[6]  A. Dalai,et al.  Syngas production through dry reforming: A review on catalysts and their materials, preparation methods and reactor type , 2022, Chemical Engineering Journal.

[7]  T. Breugelmans,et al.  Use of Nanoscale Carbon Layers on Ag-Based Gas Diffusion Electrodes to Promote CO Production , 2022, ACS Applied Nano Materials.

[8]  Douglas R. Kauffman,et al.  Resolving the Size-Dependent Transition between CO2 Reduction Reaction and H2 Evolution Reaction Selectivity in Sub-5 nm Silver Nanoparticle Electrocatalysts , 2022, ACS Catalysis.

[9]  Wuzhengzhi Zhang,et al.  Efficacious CO2 Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO2 Electroreduction to CO. , 2021, Inorganic chemistry.

[10]  T. Breugelmans,et al.  Sn-Based Electrocatalyst Stability: A Crucial Piece to the Puzzle for the Electrochemical CO2 Reduction toward Formic Acid , 2021, ACS Energy Letters.

[11]  Huiyi Li,et al.  Efficient CO2 Electroreduction via Au-Complex Derived Carbon Nanotube Supported Au Nanoclusters. , 2021, ChemSusChem.

[12]  Haocheng Xiong,et al.  Oxyhydroxide Species Enhances CO2 Electroreduction to CO on Ag via Coelectrolysis with O2 , 2021, ACS Catalysis.

[13]  J. Arbiol,et al.  Metal Oxide Clusters on Nitrogen-Doped Carbon are Highly Selective for CO2 Electroreduction to CO , 2021, ACS Catalysis.

[14]  D. Sebők,et al.  Operando cathode activation with alkali metal cations for high current density operation of water-fed zero-gap carbon dioxide electrolyzers , 2021, Nature Energy.

[15]  Christine M. Gabardo,et al.  Self-Cleaning CO2 Reduction Systems: Unsteady Electrochemical Forcing Enables Stability , 2021, ACS Energy Letters.

[16]  Jingguang G. Chen,et al.  Boosting Activity and Selectivity of CO2 Electroreduction by Pre-Hydridizing Pd Nanocubes. , 2020, Small.

[17]  Shichun Mu,et al.  Defect Engineering on Carbon-Based Catalysts for Electrocatalytic CO2 Reduction , 2020, Nano-Micro Letters.

[18]  P. Strasser,et al.  Highly selective and scalable CO2 to CO - Electrolysis using coral-nanostructured Ag catalysts in zero-gap configuration , 2020 .

[19]  Xiaoqing Pan,et al.  Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO4/SiO2 Catalysts. , 2020, Journal of the American Chemical Society.

[20]  Yifan Li,et al.  Dual-atom Ag2/graphene catalyst for efficient electroreduction of CO2 to CO , 2020 .

[21]  Jingli Luo,et al.  Hexagonal Zn nanoplates enclosed by Zn(100) and Zn(002) facets for highly selective CO2 electroreduction to CO. , 2020, ACS applied materials & interfaces.

[22]  D. Dvorak,et al.  Managing Hydration at the Cathode Enables Efficient CO2 Electrolysis at Commercially Relevant Current Densities , 2020 .

[23]  Jingguang G. Chen,et al.  Accelerating CO2 Electroreduction to CO Over Pd Single‐Atom Catalyst , 2020, Advanced Functional Materials.

[24]  Saket S. Bhargava,et al.  System Design Rules for Intensifying the Electrochemical Reduction of CO 2 to CO on Ag Nanoparticles , 2020, ChemElectroChem.

[25]  Tingting Fan,et al.  Electrochemically Driven Formation of Sponge-like Porous Ag Nanocubes toward Efficient CO2 Electroreduction to CO. , 2020, ChemSusChem.

[26]  W. Kou,et al.  Nickel–Nitrogen-Doped Three-Dimensional Ordered Macro-/Mesoporous Carbon as an Efficient Electrocatalyst for CO2 Reduction to CO , 2020 .

[27]  X. Xia,et al.  Importance of Au nanostructures in CO2 electrochemical reduction reaction. , 2020, Science bulletin.

[28]  I. Chorkendorff,et al.  Analysis of Mass Flows and Membrane Crossover in CO2 Reduction at High Current Densities in a MEA-Type Electrolyzer. , 2019, ACS applied materials & interfaces.

[29]  L. Cotarca,et al.  Phosgene , 2019, Ullmann's Encyclopedia of Industrial Chemistry.

[30]  Xiaosong Hu,et al.  Nitrogen-Doped Carbon Cages Encapsulating CuZn Alloy for Enhanced CO2 Reduction. , 2019, ACS applied materials & interfaces.

[31]  S. Suh,et al.  Climate change mitigation potential of carbon capture and utilization in the chemical industry , 2019, Proceedings of the National Academy of Sciences.

[32]  Hyunjoo J. Lee,et al.  Electrochemical CO2 reduction using alkaline membrane electrode assembly on various metal electrodes , 2019, Journal of CO2 Utilization.

[33]  A. Züttel,et al.  Boosting CO Production in Electrocatalytic CO2 Reduction on Highly Porous Zn Catalysts , 2019, ACS Catalysis.

[34]  T. Wadayama,et al.  Surface Atomic Arrangement Dependence of Electrochemical CO2 Reduction on Gold: Online Electrochemical Mass Spectrometric Study on Low-Index Au(hkl) Surfaces , 2019, ACS Catalysis.

[35]  Jingguang G. Chen,et al.  Shape‐Controlled CO2 Electrochemical Reduction on Nanosized Pd Hydride Cubes and Octahedra , 2019, Advanced Energy Materials.

[36]  F. P. García de Arquer,et al.  High Rate, Selective, and Stable Electroreduction of CO2 to CO in Basic and Neutral Media , 2018, ACS Energy Letters.

[37]  X. Bao,et al.  Carbon dioxide electroreduction over imidazolate ligands coordinated with Zn(II) center in ZIFs , 2018, Nano Energy.

[38]  Guoxiong Wang,et al.  Oxygen Vacancies in ZnO Nanosheets Enhance CO2 Electrochemical Reduction to CO. , 2018, Angewandte Chemie.

[39]  S. Karakalos,et al.  Preferentially Oriented Ag Nanocrystals with Extremely High Activity and Faradaic Efficiency for CO2 Electrochemical Reduction to CO. , 2018, ACS applied materials & interfaces.

[40]  S. Qiao,et al.  Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO2 , 2017 .

[41]  W. Chu,et al.  Exclusive Ni-N4 Sites Realize Near-Unity CO Selectivity for Electrochemical CO2 Reduction. , 2017, Journal of the American Chemical Society.

[42]  Jeremy T. Feaster,et al.  Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes , 2017 .

[43]  D. Gu,et al.  Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics. , 2016, Angewandte Chemie.

[44]  C. Friend,et al.  Achieving Selective and Efficient Electrocatalytic Activity for CO2 Reduction Using Immobilized Silver Nanoparticles. , 2015, Journal of the American Chemical Society.

[45]  A. Hubin,et al.  N-doped ordered mesoporous carbons prepared by a two-step nanocasting strategy as highly active and selective electrocatalysts for the reduction of O2 to H2O2 , 2015 .

[46]  F. Calle‐Vallejo,et al.  Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide. , 2015, The journal of physical chemistry letters.

[47]  S. Back,et al.  Active Sites of Au and Ag Nanoparticle Catalysts for CO2 Electroreduction to CO , 2015 .

[48]  Paul J. A. Kenis,et al.  Influence of dilute feed and pH on electrochemical reduction of CO2 to CO on Ag in a continuous flow electrolyzer , 2015 .

[49]  P. Ajayan,et al.  Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes. , 2015, ACS nano.

[50]  P. Kenis,et al.  Nanoparticle Silver Catalysts That Show Enhanced Activity for Carbon Dioxide Electrolysis , 2013 .

[51]  Christos T. Maravelias,et al.  Fuel production from CO2 using solar-thermal energy: system level analysis , 2012 .

[52]  Y. Shim,et al.  Ag(I)-cysteamine complex based electrochemical stripping immunoassay: ultrasensitive human IgG detection. , 2011, Biosensors & bioelectronics.

[53]  George C. Schatz,et al.  Reversing the size-dependence of surface plasmon resonances , 2010, Proceedings of the National Academy of Sciences.

[54]  R. Prins,et al.  Basic Metal Oxides as Cocatalysts for Cu/SiO2Catalysts in the Conversion of Synthesis Gas to Methanol , 1998 .

[55]  Guoxiong Wang,et al.  Tailoring the interactions of heterogeneous Ag2S/Ag interface for efficient CO2 electroreduction , 2021 .

[56]  A. Świątkowski,et al.  Evaluation of different carbon materials in adsorption and solid-phase microextraction of 2,4,6-trichlorophenol from water , 2019, DESALINATION AND WATER TREATMENT.

[57]  Guenter Schmid,et al.  Technical photosynthesis involving CO2 electrolysis and fermentation , 2018, Nature Catalysis.

[58]  Glenn J. Sunley,et al.  Methanol carbonylation revisited: thirty years on. , 1996 .