An air-stable, reusable Ni@Ni(OH)<sub>2</sub>nanocatalyst for CO<sub>2</sub>/bicarbonate hydrogenation to formate

Fu, Xin-Pu; Peres, Laurent; Esvan, Jérôme; Amiens, Catherine; Philippot, Karine; Yan, Ning

doi:10.1039/d1nr01054a

Cited by 20 publications

(21 citation statements)

References 70 publications

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“…Then, the valence states of Ni and Co on the surface of the fresh and spent Ni 3 Co 1 @NC and Ni 3 Co 1 @NC-P catalysts were investigated by XPS to confirm the influence of surface properties on the catalytic performance (Figures and S14). As shown in Figure a, the Ni species of the fresh Ni 3 Co 1 @NC sample can be fitted to four peaks at about 853.0, 854.4, 856.4, and 860.3 eV, and they were ascribed to Ni 0 , NiO, Ni(OH) 2 , and Ni satellite peaks, respectively. − The amount of Ni 0 species decreased from 44.1 to 26.4% after the fourth recycle test, indicating that oxidation of Ni species occurs during the tandem hydrogenation reaction. However, for the Ni 3 Co 1 @NC-P sample, the amount of Ni 0 species decreased from 47.8 to 38.7% after five runs.…”

Section: Resultsmentioning

confidence: 94%

Tuning the Surface Alloy Composition of Phosphorus-Promoted Ni–Co Bimetallic Nanoparticles for Selective Tandem Hydrogenation

Dong

Guo

et al. 2023

ACS Catal.

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Selective tandem hydrogenation is a promising strategy for catalytic conversion of bulk raw materials with multifunctional groups into high-value-added chemicals via multiple-step reactions. Yet now, one of the current challenges is to develop a multifunctional and stable catalyst enabling the tandem catalysis rather than interrupting at any step reaction, particularly for supported nonprecious metal catalysts. In this work, we report tandem hydrogenation of bulk phthalic anhydride toward the one-pot synthesis of hexahydrophthalide, an emerging monomer of a recyclable polyester, over phosphorus-promoted Ni–Co bimetallic alloy nanoparticle catalysts. The surface composition of catalysts can be easily regulated by changing the Ni/Co molar ratio and the phosphorous functionalization strategy, which could then tune the product selectivity and enhance the stability of this tandem process. The optimal Ni3Co1@NC-P affords 88% selectivity for the desired product and demonstrates promising stability toward the tandem hydrogenation reaction. Systematic experimental and computational studies reveal that the adsorption strength of the intermediates and the ability of hydrogen activation can be altered by the formation of surface metallic Ni species, thus tuning the product selectivity. In addition, the oxidation resistance of Ni3Co1@NC-P was enhanced by the phosphorization treatment, which makes the bimetallic alloy successfully realize the tandem hydrogenation reaction. The finding of this work not only provides a convenient strategy to design and develop efficient and stable non-noble metal-based catalysts for selective tandem hydrogenation reactions, especially involving the hydrodeoxygenation reaction, but also fulfills the straightforward pathway for the preparation of degradable polyester monomer hexahydrophthalide.

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Section: Resultsmentioning

confidence: 94%

Tuning the Surface Alloy Composition of Phosphorus-Promoted Ni–Co Bimetallic Nanoparticles for Selective Tandem Hydrogenation

Dong

Guo

et al. 2023

ACS Catal.

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“…In conclusion, the design of efficient catalysts for CO 2 hydrogenation heavily relies on a deep understanding of the structure–activity correlation and the mechanistic principles guiding the reaction. For CO 2 hydrogenation to formic acid/formate, we have identified the crucial role of electron-enriched metal active sites for hydrogen splitting and a sufficient number of weak basic sites for CO 2 activation. , This understanding leads to the development of encapsulated Pd-based bimetallic cluster catalysts within porous silica materials exhibiting considerable activity enhancements. , Furthermore, the successful application of non-noble Ni@Ni(OH) 2 nanocatalysts highlights the potential for low-cost and sustainable catalyst systems . Moving forward, several research directions may be worth pursuing: 1) continuing to improve catalyst design principles and exploring new types of catalysts; 2) developing inexpensive metal-based catalysts as alternatives to noble metals like Pd with no or little compromise of the catalytic performance.…”

Section: Discussionmentioning

confidence: 99%

“…Drawing inspiration from the encapsulation design concept, we successfully employed air-stable and reusable non-noble Ni@ Ni(OH) 2 nanocatalysts for CO 2 /bicarbonate hydrogenation to formate. 17 These nanocatalysts were prepared using a one-step organometallic method, which offers a promising approach for the creation of structurally well-defined catalysts. By controlling the decomposition of the organometallic bis-(cyclooctadiene) nickel(0) complex, nickel nanoparticles with a controlled surface composition were constructed with the help of ligands and solvents (THF/EtOH).…”

Section: "Encapsulated" Ni Catalyst For Co 2 Hydrogenation To Formatementioning

confidence: 99%

Mechanism-Guided Catalyst Design for CO₂ Hydrogenation to Formate and Methanol

et al. 2023

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Metrics & MoreArticle Recommendations CONSPECTUS: CO 2 to formate/formic acid and methanol has emerged as a promising method for utilizing CO 2 in chemical and fuel synthesis, as well as reducing CO 2 emissions when H 2 is produced through renewable energy sources. This reaction requires the activation of two chemically distinct molecules, CO 2 and H 2 , along with the selective formation of the desired product.Creating efficient catalysts that surpass the limitations of existing catalysts remains a significant challenge. Historically, the development of catalysts has largely depended on trial and error until successful outcomes are achieved. However, recent advances in material synthesis for well-defined structures, reaction kinetics analysis, in situ characterization techniques, and computational studies have facilitated a systematic understanding of catalytic reactions and enabled mechanism-guided catalyst development. This innovative approach has empowered researchers to strategically design effective catalysts that optimize the target reaction, particularly the rate-determining step, while tackling other limitations, such as selectivity and stability. This Account provides an overview of our recent efforts in catalyst development for CO 2 hydrogenation through mechanism-guided engineering, which are primarily divided into two sections: (i) formic acid/formate and (ii) methanol production. For the CO 2 hydrogenation to formate/formic acid, we first discuss the structure−activity correlation studies of various metal/support catalyst systems, including different metal particle sizes, types of support, and crystalline morphologies of the support. These studies highlight the crucial role of electron-rich metal sites for H 2 splitting and an adequate number of weak basic sites for CO 2 activation, which inform the design of improved catalysts with unique architectures. Notably, encapsulated metal cluster catalysts enhance the utilization of metal species and optimize the synergistic interaction between metal active sites and the support material. The encapsulation strategy can also be applied to inexpensive metal elements such as Ni, facilitating the development of highly efficient catalysts. Our primary focus for CO 2 -to-methanol catalysts is the design of active and durable oxide-based catalysts. We first identify that the critical limitation of metal oxide catalysts is their poor H 2 activation capability, based on a comprehensive review of classical and state-of-the-art understanding of the CO 2 -to-methanol catalysts. Consequently, the principal catalyst design concept involves coupling metal promoters, which provide high H 2 activation functionality, with metal oxide catalysts that enable the adsorption of CO 2 and selective methanol synthesis. An essential synthetic approach is the doping of metal promoters on the surface of oxide catalysts. Specifically, atomically dispersed metal promoters significantly improve methanol yield by maximizing interfacial synergy with the oxide catalyst. A remarkable strateg...

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“…The ever-increasing worldwide consumption of fossil fuels has increased the emission of the greenhouse gas, carbon dioxide . Artificial photosynthesis for CO 2 conversion to fuels and value-added chemicals on light-responsive semiconductors is an intriguing strategy for remediating global climate changes and alleviating high chemical energy demand. − In complicated photocatalytic CO 2 reduction systems, ideal catalysts are desirable to feature good ability for light-harvesting and excellent electron transfer as well as to provide abundant active sites to encompass enzyme-like catalytic CO 2 conversion with high activity and selectivity. Among various photocatalysts, heptazine-based polymers, with tunable C/N atomic ratio and electronic structure, are a class of promising candidates for photocatalytic CO 2 conversion because of their low cost, high chemical stability, and good visible light response. − Nevertheless, two major shortcomings lead to extremely low performance on CO 2 reduction.…”

Section: Introductionmentioning

confidence: 99%

Edge Engineering of Carbon Nitride Nanodots with Pocket-like Sites for Effective Photoreduction of Bicarbonate to CO under Visible Light

Liu

Zhang

Liu

et al. 2023

ACS Appl. Eng. Mater.

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Abundant pocket-like defects are engineered on the edge of carbon nitride nanodots (CN1.9), using hydrazine groups to attack carbon atoms which results in CN heterocycle opening of porous graphitic C3N4. These edge defects on CN1.9 not only modulate the electronic structure, extend light absorption, and promote photoexcited electron transfer but also lead to c(HCO3 –)/c(CO2, aq)-dependent photocatalytic CO evolution in CO2 bubbling HCO3 – aqueous solution (pH ≈ 7.1∼7.5). Even in the N2/HCO3 – system (pH ≈ 8.17), wherein c(HCO3 –) is about 67 times higher than c(CO2, aq), the CO production also attains 48.6 μmol g–1 h–1 on CN1.9. In the same experimental condition, almost no CO produces except for H2 on graphitic carbon nitride (GCN). DFT theoretical calculation reveals that edge defects prefer to contact with HCO3 – and proton to orient a special reaction pathway of HCO3* → H2CO3* → CO on CN1.9 with a relatively low-energy barrier rather than HCO3* → H2O–CO2* → CO on GCN.

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An air-stable, reusable Ni@Ni(OH)₂nanocatalyst for CO₂/bicarbonate hydrogenation to formate

Abstract: Production of formate via CO2/bicarbonate hydrogenation using cheap metal-based heterogeneous catalysts is attractive. Herein, we report the organometallic synthesis of a foam-like Ni@Ni(OH)2 composite nanomaterial which exhibited remarkable air stability...

Cited by 20 publications

References 70 publications

Tuning the Surface Alloy Composition of Phosphorus-Promoted Ni–Co Bimetallic Nanoparticles for Selective Tandem Hydrogenation

Tuning the Surface Alloy Composition of Phosphorus-Promoted Ni–Co Bimetallic Nanoparticles for Selective Tandem Hydrogenation

Mechanism-Guided Catalyst Design for CO₂ Hydrogenation to Formate and Methanol

Edge Engineering of Carbon Nitride Nanodots with Pocket-like Sites for Effective Photoreduction of Bicarbonate to CO under Visible Light

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An air-stable, reusable Ni@Ni(OH)2nanocatalyst for CO2/bicarbonate hydrogenation to formate

Abstract: Production of formate via CO2/bicarbonate hydrogenation using cheap metal-based heterogeneous catalysts is attractive. Herein, we report the organometallic synthesis of a foam-like Ni@Ni(OH)2 composite nanomaterial which exhibited remarkable air stability...

Cited by 20 publications

References 70 publications

Tuning the Surface Alloy Composition of Phosphorus-Promoted Ni–Co Bimetallic Nanoparticles for Selective Tandem Hydrogenation

Tuning the Surface Alloy Composition of Phosphorus-Promoted Ni–Co Bimetallic Nanoparticles for Selective Tandem Hydrogenation

Mechanism-Guided Catalyst Design for CO2 Hydrogenation to Formate and Methanol

Edge Engineering of Carbon Nitride Nanodots with Pocket-like Sites for Effective Photoreduction of Bicarbonate to CO under Visible Light

Contact Info

Product

Resources

About

An air-stable, reusable Ni@Ni(OH)₂nanocatalyst for CO₂/bicarbonate hydrogenation to formate

Mechanism-Guided Catalyst Design for CO₂ Hydrogenation to Formate and Methanol