Atomically dispersed single Ni site catalysts for high-efficiency CO<sub>2</sub> electroreduction at industrial-level current densities

Li, Yang; Adli, Nadia Mohd; Shan, Weitao; Wang, Maoyu; Zachman, Michael J.; Hwang, Sooyeon; Tabassum, Hassina; Karakalos, Stavros; Feng, Zhenxing; Wang, Guofeng; Li, Chris; Wu, Gang

doi:10.1039/d2ee00318j

Cited by 160 publications

(114 citation statements)

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“…Reducing CO 2 toward the generation of valuable chemicals is one of the important strategies to achieve the dual carbon goal. 177 , 178 Wang et al. presented a carbon-confined indium oxide electrocatalyst for efficient CO 2 RR toward the direct production of formic acid.…”

Section: Applications Of Mof Nanocrystal-derived Hollow Porous Materialsmentioning

confidence: 99%

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

et al. 2022

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Section: Applications Of Mof Nanocrystal-derived Hollow Porous Materialsmentioning

confidence: 99%

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

et al. 2022

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“…Single-atom catalysts (SACs) have drawn increasing attention in the field of catalysis thanks to the maximum utilization efficiency of atomically dispersed metals and their unsaturated coordination. [71][72][73][74][75] To prepare SACs, support is necessary to anchor and stabilize monodispersed metal sites. [76][77][78] Functional carbon has been widely demonstrated to be a type of suitable support for hosting single-atom metals due to its enhanced stabilization effects (Figure 4A).…”

Section: Single Metal Sitesmentioning

confidence: 99%

“…The GDE-based flow cells and MEA fuel cells are promising prototype reactors to achieve high-rate CO 2 reduction with industry-level currents, especially when combined with an anion exchange membrane. [75,185,186] However, most carbonbased catalysts were measured in H-type cells; future activity needs to be evaluated in flow cells and/or acual electrolyzers to evaluate their industry-level performance. In addition, how configurations of GDE, electrolyte, membrane, and size of reactor impact CO 2 RR performance remains not well understood, which should be further evaluated to establish optimal working conditions with enhanced energy conversion efficiency.…”

Section: Development Of Advanced Electrolyzersmentioning

confidence: 99%

Carbon Catalysts for Electrochemical CO₂ Reduction toward Multicarbon Products

Pan

Yang

O'Carroll

et al. 2022

Advanced Energy Materials

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chemicals has been emerging as one of the most attractive routes by the aqueous medium system and convenient operation under ambient conditions. [1,2] Moreover, CO 2 electrolysis can be powered by renewable energy-derived electricity, offering a viable route to store intermittent renewable energy into transportable fuels.CO 2 reduction reaction (CO 2 RR) at the cathode is the critical process in CO 2 electrolysis (Figure 1A), which takes place at a complex solid/liquid/gas triple-phase interface (Figure 1B). [3] Solid-state electrocatalysts are at the heart of CO 2 electrolysis technology, determining activity, selectivity, stability, and energy conversion efficiency. Theoretically, CO 2 RR can produce a broad distribution of products ranging from C 1 (e.g., CO, HCOOH) to C 2 (e.g., C 2 H 4 , CH 3 COOH, C 2 H 5 OH) and C 3 (e.g., CH 3 COCH 3 , C 3 H 7 OH) (Figure 1C). [4] To meet the criteria for practical implementation, techno-economic analyses suggest that CO 2 electrolysis should produce a single product with a Faradaic efficiency (FE) > 90%, a partial current density (J p ) > 200 mA cm −2 , an energy conversion efficiency (EE) > 60%, and operation stability of more than 1000 h. [1,5,6] Figure 1D summarizes the current benchmarking performance for typical products. Obviously, the reduction of CO 2 to CO on commercial silver nanoparticles [7] and HCOOH on defective bismuth oxide nanotubes [8] are close to industrial thresholds and under pilot-scale test, [2] despite the short operation time for HCOOH provided in the literature.Compared to C 1 , reducing CO 2 to C 2+ hydrocarbons and oxygenates is more desirable because of their higher energy density, larger market size, and bigger contribution to decreasing net CO 2 emission. [1] However, the current CO 2 -to-C 2+ system remains far from meeting the thresholds necessary for practical application, especially with regard to FE, EE, and stability (Figure 1D). For example, the state-of-the-art CO 2 -to-C 2 H 4 reduction displays an FE of 80% and a J p of 400 mA cm −2 for 100 h on copper-aluminum alloy in a gas diffusion electrode (GDE)-based flow cell electrolyzer using 1 m KOH electrolyte, [9] or longer durability (150 h) yet a lower FE (70%) and J p (100 mA cm −2 ) on metallic copper in a flow cell with 7 m KOH electrolyte. [10] The best CO 2 -to-C 2 H 5 OH catalyst presents an FE of 52%, a J p of 160 mA cm −2 , and a EE of 16% for 16 h on carbon-coated copper fiber in a GDE-based membrane electrode assembly (MEA) fuel cell electrolyzer using humidified Electrochemical CO 2 reduction offers a compelling route to mitigate atmospheric CO 2 concentration and store intermittent renewable energy in chemical bonds. Beyond C 1 , C 2+ feedstocks are more desirable due to their higher energy density and more significant market need. However, the CO 2 -to-C 2+ reduction suffers from significant barriers of CC coupling and complex reaction pathways. Due to remarkable tunability over morphology/pore architecture along with great feasibility of functionalization to modify t...

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“…Ni. [17][18][19][20][21][22][23][24][25] Recent studies have reported that an unsaturated coordinated NiNC catalyst with a broken D 4h symmetry is more optimized for the CO 2 RR than Ni-N 4 with the D 4h square-planar geometry. [26][27][28][29][30] The optimized electronic structure of Ni single atoms is significantly converted from that of bulk Ni, exhibiting high H* chemisorption energy and low energy barrier for CO 2 activation.…”

Section: (2 Of 9)mentioning

confidence: 99%

“…[ 4,15,16 ] Generally, a NiNC catalyst has a structure in which a support N atoms surrounds the center of a single Ni atom, exhibiting outstanding catalytic activity, unlike bulk Ni. [ 17–25 ] Recent studies have reported that an unsaturated coordinated NiNC catalyst with a broken D 4h symmetry is more optimized for the CO 2 RR than Ni‐N 4 with the D 4h square‐planar geometry. [ 26–30 ] The optimized electronic structure of Ni single atoms is significantly converted from that of bulk Ni, exhibiting high H* chemisorption energy and low energy barrier for CO 2 activation.…”

Section: Introductionmentioning

confidence: 99%

Real‐Time Mimicking the Electronic Structure of N‐Coordinated Ni Single Atoms: NiS‐Enabled Electrochemical Reduction of CO₂ to CO

Han

Kim

et al. 2022

Advanced Energy Materials

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as a side reaction, thereby diminishing the selectivity of the CO 2 RR. To increase the selectivity and catalytic activity of the CO 2 RR, several materials, such as Ag, Cu, Au, Sn, N-coordinated Ni single atoms (NiNC), FeNC, and so on have been reported as electrochemical catalysts. [4][5][6][7][8][9][10][11][12] These catalysts possess high H* chemisorption energies and moderate *COOH chemisorption energies, suppressing the HER and accelerating formation of carbonaceous products. In contrast, other materials such as bulk Ni and Pt have low H* chemisorption energies, exhibiting small kinetic barrier and high selectivity for the HER. [2,13,14] Single-atom catalysts have attracted significant attention from researchers because their properties significantly differ from those of bulk materials. Many previous studies focused on determining efficient designs of single-atom catalysts to maximize their activity. [4,15,16] Generally, a NiNC catalyst has a structure in which a support N atoms surrounds the center of a single Ni atom, exhibiting outstanding catalytic activity, unlike bulk N-coordinated Ni single atom (Ni-NC) is one of the best catalysts for the CO 2 reduction reaction (CO 2 RR) to produce CO. However, no bulk Ni materials have exhibited high catalytic activity for CO 2 RR. Herein, it is shown that NiS nanoparticles mimicking the electronic structure of Ni-NC in real-time enhance the CO 2 RR activity in a zero-gap electrolyzer. In situ/Operando X-ray absorption spectroscopy suggests that under a cathodic potential, the electronic structure of NiS changes similarly to that of Ni-NC and modulated O x-z S y ligands with similar properties to Ni ligands, resulting in a mimicked electronic structure. However, NiS exhibits low stability owing to the loss of S species, key to mimicking N ligands. The future challenges in finding a stable mimicked electronic structure are discussed. Moreover, this work provides new insights into the development of catalysts from materials that have not generally been considered previously.

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Atomically dispersed single Ni site catalysts for high-efficiency CO₂ electroreduction at industrial-level current densities

Abstract: Atomically dispersed and nitrogen-coordinated single Ni sites (i.e., NiNx moieties) embedded in partially graphitized carbon have emerged as effective catalysts for CO2 electroreduction to CO. However, much mystery remains behind...

Cited by 160 publications

References 60 publications

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

Carbon Catalysts for Electrochemical CO₂ Reduction toward Multicarbon Products

Real‐Time Mimicking the Electronic Structure of N‐Coordinated Ni Single Atoms: NiS‐Enabled Electrochemical Reduction of CO₂ to CO

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Atomically dispersed single Ni site catalysts for high-efficiency CO2 electroreduction at industrial-level current densities

Abstract: Atomically dispersed and nitrogen-coordinated single Ni sites (i.e., NiNx moieties) embedded in partially graphitized carbon have emerged as effective catalysts for CO2 electroreduction to CO. However, much mystery remains behind...

Cited by 160 publications

References 60 publications

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

Carbon Catalysts for Electrochemical CO2 Reduction toward Multicarbon Products

Real‐Time Mimicking the Electronic Structure of N‐Coordinated Ni Single Atoms: NiS‐Enabled Electrochemical Reduction of CO2 to CO

Contact Info

Product

Resources

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Atomically dispersed single Ni site catalysts for high-efficiency CO₂ electroreduction at industrial-level current densities

Carbon Catalysts for Electrochemical CO₂ Reduction toward Multicarbon Products

Real‐Time Mimicking the Electronic Structure of N‐Coordinated Ni Single Atoms: NiS‐Enabled Electrochemical Reduction of CO₂ to CO