Delocalization state-induced selective bond breaking for efficient methanol electrosynthesis from CO2

Kong, Sijia; Lv, Ximeng; Wang, Xin; Liu, Zhengzheng; Li, Zichuang; Jia, Baoping; Sun, Du; Yang, Chao; Liu, Lijia; Guan, Anxiang; Wang, Yuandong; Zheng, Gengfeng; Huang, Fuqiang

doi:10.1038/s41929-022-00887-z

Cited by 79 publications

(66 citation statements)

References 54 publications

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“…Lower panel: On a softer acid site (e.g., Cu 2 NCN), the Δ H Cu–O can be tuned into a value lower than Δ H O–C , which breaks the Cu–O bond to release *OCH 3 and enhances the CO 2 -to-CH 3 OH selectivity. Reproduced with permission from ref . Copyright 2023 The Authors.…”

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

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Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

Liu

Yang

et al. 2023

Acc. Mater. Res.

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Conspectus The carbon balance has been disrupted by the widespread use of fossil fuels and subsequent excessive emissions of carbon dioxide (CO2), which has become an increasingly critical environmental challenge for human society. The production and use of renewable energy sources and/or chemicals have been proposed as important strategies to reduce emissions, of which the electrochemical CO2 (or CO) reduction reaction (CO2RR/CORR) in the aqueous systems represents a promising approach. Benefitted by the capacity of manufacturing high-value-added products (e.g., ethylene, ethanol, formic acid, etc.) with a net-zero carbon emission, copper-based CO2RR/CORR powered by sustainable electricity is regarded as a potential candidate for carbon neutrality. However, the diversity of selectivities in copper-based systems poses a great challenge to the research in this field and sets a great obstacle for future industrialization. To date, scientists have revealed that the electrocatalyst design and preparation play a significant role in achieving efficient and selective CO2-to-chemical (or CO-to-chemical) conversion. Although substantial efforts have been dedicated to the catalyst preparation and corresponding electrosynthesis of sustainable chemicals from CO2/CO so far, most of them are still derived from empirical or random searches, which are relatively inefficient and cost-intensive. Most of the mechanism studies have suggested that both intrinsic properties (such as electron states) and extrinsic environmental factors (such as surface energy) of a catalyst can significantly alter catalytic performance. Thus, these two topics are mainly discussed for copper-based catalyst developments in this Account. Here, we provided a concise and comprehensive introduction to the well-established strategies employed for the design of copper-based electrocatalysts for CO2RR/CORR. We used several examples from our research group, as well as representative studies of other research groups in this field during the recent five years, with the perspectives of tuning local electron states, regulating alloy phases, modifying interfacial coverages, and adjusting other interfacial microenvironments (e.g., molecule modification or surface energy). Finally, we employed the techno-economic assessment with a viewpoint on the future application of CO2/CO electroreduction in manufacturing sustainable chemicals. Our study indicates that when carbon price is taken into account, the electrocatalytic CO2-to-chemical conversion can be more market-competitive, and several potential value-added products including formate, methanol, ethylene, and ethanol can all make profits under optimal operating conditions. Moreover, a downstream module employing traditional chemical industrial processes (e.g., thermal polymerization, catalytic hydrolysis, or condensation process) will also make the whole electrolysis system profitable in the future. These design principles, combined with the recent advances in the development of efficient copper-based electrocatalysts,...

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Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

Section: Recent Developments Of Cu-based Catalysts On Intrinsic Prope...mentioning

confidence: 99%

See 2 more Smart Citations

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

Liu

Yang

et al. 2023

Acc. Mater. Res.

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“…To this end, we are motivated to design such an efficient electrochemical device. For the cathodic CO 2 RR, various high-valued C 1 or C 2 products, i.e ., formic acid, methanol, ethanol, etc ., have been generated; , however, large overpotentials are required, which would reduce the output voltage of the metal–CO 2 battery. The CO 2 -to-CO process involves 2e – transfer, and occurs at a fairly low overpotential, and the reaction kinetics is relatively fast, which are the critical factors for the cathodic reaction to achieve a high-performance battery.…”

Section: Introductionmentioning

confidence: 99%

One Stone Three Birds: An Aqueous Mg–CO₂ Battery for Generation of Electricity, Syngas, and High-Value Phosphate

Chen

Wang

Fan

et al. 2023

ACS Sustainable Chem. Eng.

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Mg–CO2 battery as a promising strategy for CO2 conversion and utilization is challenging, owing to the sluggish kinetics of CO2 reduction reaction (CO2RR) and the waste of the sacrificial Mg anode. Herein, by elaborately designing a highly selective Ni NPs/Ni–N–C SACs electrocatalyst toward CO2RR and rationally optimizing the electrolyte, an effective aqueous-phase Mg–CO2 battery is demonstrated to generate not only electricity, but also syngas with CO from the CO2RR and H2 from the chemical oxidation of Mg, together with higher-valued MgHPO4 phosphate. Notably, the output of electricity, the proportion of CO/H2 in syngas, and the yields/crystalline quality of MgHPO4 can be well regulated by manipulating the operation parameters. The Mg–CO2 battery generates a favorable open-circuit voltage of 1.44 V with a peak power density of 2.91 mW cm–2. Under the optimal condition, the Ni NPs/Ni–N–C SACs catalyst displays both a high FECO of 98.12% at −0.573 VRHE and a high CO2-to-CO current of −20.73 mA cm–2 at −0.973 VRHE, owing to the synergistic effect between Ni particles and Ni–N moieties. The proposed Mg–CO2 battery provides an intriguing approach for CO2 conversion and utilization in off-grid, with the advantage of coproduction of higher-valued chemicals at both electrodes.

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Intercalative Motifs‐Induced Space Confinement and Bonding Covalency Enhancement Enable Ultrafast and Large Sodium Storage

Peng

et al. 2023

Adv Funct Materials

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Alloying-type metal sulfides with high theoretical capacities are promising anodes for sodium-ion batteries, but suffer from sluggish sodiation kinetics and huge volume expansion. Introducing intercalative motifs into alloyingtype metal sulfides is an efficient strategy to solve the above issues. Herein, robust intercalative InS motifs are grafted to high-capacity layered Bi 2 S 3 to form a cation-disordered (BiIn) 2 S 3 , synergistically realizing high-rate and large-capacity sodium storage. The InS motif with strong bonding serves as a space-confinement unit to buffer the volume expansion, maintaining superior structural stability. Moreover, the grafted high-metallicity Indium increases the bonding covalency of BiS, realizing controllable reconstruction of BiS bond during cycling to effectively prevent the migration and aggregation of atomic Bi. The novel (BiIn) 2 S 3 anode delivers a high capacity of 537 mAh g −1 at 0.4 C and a superior high-rate stability of 247 mAh g −1 at 40 C over 10000 cycles. Further in situ and ex situ characterizations reveal the in-depth reaction mechanism and the breakage and formation of reversible BiS bonds. The proposed space confinement and bonding covalency enhancement strategy via grafting intercalative motifs can be conducive to developing novel high-rate and large-capacity anodes.

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Delocalization state-induced selective bond breaking for efficient methanol electrosynthesis from CO2

Cited by 79 publications

References 54 publications

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

One Stone Three Birds: An Aqueous Mg–CO₂ Battery for Generation of Electricity, Syngas, and High-Value Phosphate

Intercalative Motifs‐Induced Space Confinement and Bonding Covalency Enhancement Enable Ultrafast and Large Sodium Storage

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Delocalization state-induced selective bond breaking for efficient methanol electrosynthesis from CO2

Cited by 79 publications

References 54 publications

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO2 and CO Electroreduction

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO2 and CO Electroreduction

One Stone Three Birds: An Aqueous Mg–CO2 Battery for Generation of Electricity, Syngas, and High-Value Phosphate

Intercalative Motifs‐Induced Space Confinement and Bonding Covalency Enhancement Enable Ultrafast and Large Sodium Storage

Contact Info

Product

Resources

About

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

One Stone Three Birds: An Aqueous Mg–CO₂ Battery for Generation of Electricity, Syngas, and High-Value Phosphate