Construction of defective cobalt oxide for methane combustion by oxygen vacancy engineering

Zhang, Xin; Jin, Xin; Bao, Liurui; Zhang, Mingchao; Song, Ruiming; Yu, Wei; Huang, Wei; Su, Weiguang; Li, Xingyun

doi:10.1039/d1nj01296g

Cited by 10 publications

(8 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The low-temperature methane activation contributes to numerous catalytic methane reactions, where the rate-determining step is the first C–H bond dissociation step of the methane molecule. Co 3 O 4 is widely used as a catalyst for methane combustion. , As an example of the potential applications, the catalytic property of MB-Co 3 O 4 was studied for methane catalytic combustion and compared with nano-Co 3 O 4 and submicro-Co 3 O 4 particles (Figure S15). The activity of MB-Co 3 O 4 is much higher than those of nano-Co 3 O 4 and submicro-Co 3 O 4 (Figure A and Table S2).…”

Section: Results and Discussionmentioning

confidence: 99%

“…Co 3 O 4 is widely used as a catalyst for methane combustion. 37,38 As an example of the potential applications, the catalytic property of MB-Co 3 O 4 was studied for methane catalytic combustion and compared with nano-Co 3 O 4 and submicro-Co 3 O 4 particles (Figure S15). The activity of MB-Co 3 O 4 is much higher than those of nano-Co 3 O 4 and submicro-Co 3 O 4 (Figure 3A and Table S2).…”

Section: And S11mentioning

confidence: 99%

“…24,25 The catalytic activity of MB-Co 3 O 4 is comparable to other highly active Co 3 O 4 catalysts under similar reaction conditions (Table S2). 37,38 For example, the defective Co 3 O 4 catalyst (D-Co 3 O 4 ) delivered a remarkable activity as MOC with a 50% methane conversion temperature (T 50 ) of 336 °C and a T 90 of 424 °C in 2 vol % CH 4 , which are 47 and 35 °C lower than those of the pristine Co 3 O 4 catalyst, respectively. 37 It should be noticed that the surface ignition temperature generally decreases with increasing fuel-to-air equivalence ratio.…”

Section: And S11mentioning

confidence: 99%

See 2 more Smart Citations

Co³⁺–O Bond Elongation Unlocks Co₃O₄ for Methane Activation under Ambient Conditions

Wen

Che

et al. 2022

ACS Catal.

View full text Add to dashboard Cite

The pursuit of low-temperature methane activation is a paramount challenge for heterogeneous catalysis because of the high stability of the C–H bonds (435 kJ mol–1). Very few catalysts fulfill this through either constructing complex interfaces or using special noble metal oxides. Bond length, which is highly temperature-sensitive, has long been ignored in catalyst studies. Here, we exploit a bond-length elongation strategy to unlock a nonprecious metal oxide for dissociating methane at normal temperature and pressure. Mesoporous bubblelike Co3O4 with elongated Co3+–O bonds, synthesized through a unique “melting–foaming–solidifying” route, is found to activate methane at room temperature to form CO x species on the very surface revealed by temperature-programmed reaction spectroscopy experiments. A combination of experimental and theoretical methods suggests that the elongated Co3+–O bonds contribute to the greatly enhanced methane adsorption, in contrast to the weak adsorption of methane on conventional nonprecious metal oxides. Accordingly, the activation energy for the C–H bond cleavage is smaller than that for methane desorption, which finally leads to the low-temperature methane activation. The simultaneous enhancement in intrinsic activity and mass transfer endows mesoporous bubblelike Co3O4 with excellent catalytic activity for methane combustion, where the complete conversion temperature is much below that over the conventional Co3O4 nanocatalysts.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Section: And S11mentioning

confidence: 99%

Section: And S11mentioning

confidence: 99%

See 1 more Smart Citation

Co³⁺–O Bond Elongation Unlocks Co₃O₄ for Methane Activation under Ambient Conditions

Wen

Che

et al. 2022

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…CH 4 is the cleanest fossil fuel with the highest energy content (50–55 MJ/kg) among all sources. It emits 50–60% less CO 2 , ∼ 80% less nitrogen oxides (NO x ), and almost negligible amount of toxic air pollutants including SO x , Hg, and PM 2.5 compared to that of coals ( He L. et al, 2020 ; Zhang et al, 2021 ). Today, it has been well recognized that CH 4 will play an indispensable role in the paradigm shift to a more sustainable planet.…”

Section: Introductionmentioning

confidence: 99%

Recent progress of catalytic methane combustion over transition metal oxide catalysts

et al. 2022

View full text Add to dashboard Cite

Methane (CH4) is one of the cleanest fossil fuel resources and is playing an increasingly indispensable role in our way to carbon neutrality, by providing less carbon-intensive heat and electricity worldwide. On the other hand, the atmospheric concentration of CH4 has raced past 1,900 ppb in 2021, almost triple its pre-industrial levels. As a greenhouse gas at least 86 times as potent as carbon dioxide (CO2) over 20 years, CH4 is becoming a major threat to the global goal of deviating Earth temperature from the +2°C scenario. Consequently, all CH4-powered facilities must be strictly coupled with remediation plans for unburned CH4 in the exhaust to avoid further exacerbating the environmental stress, among which catalytic CH4 combustion (CMC) is one of the most effective strategies to solve this issue. Most current CMC catalysts are noble-metal-based owing to their outstanding C–H bond activation capability, while their high cost and poor thermal stability have driven the search for alternative options, among which transition metal oxide (TMO) catalysts have attracted extensive attention due to their Earth abundance, high thermal stability, variable oxidation states, rich acidic and basic sites, etc. To date, many TMO catalysts have shown comparable catalytic performance with that of noble metals, while their fundamental reaction mechanisms are explored to a much less extent and remain to be controversial, which hinders the further optimization of the TMO catalytic systems. Therefore, in this review, we provide a systematic compilation of the recent research advances in TMO-based CMC reactions, together with their detailed reaction mechanisms. We start with introducing the scientific fundamentals of the CMC reaction itself as well as the unique and desirable features of TMOs applied in CMC, followed by a detailed introduction of four different kinetic reaction models proposed for the reactions. Next, we categorize the TMOs of interests into single and hybrid systems, summarizing their specific morphology characterization, catalytic performance, kinetic properties, with special emphasis on the reaction mechanisms and interfacial properties. Finally, we conclude the review with a summary and outlook on the TMOs for practical CMC applications. In addition, we also further prospect the enormous potentials of TMOs in producing value-added chemicals beyond combustion, such as direct partial oxidation to methanol.

show abstract

“…Thus, transition metal oxide catalysts have been used widely, though they are slightly less active on most occasions. Common transition metal oxide catalysts mainly include manganese, 2,14-19 cobalt, 10,[20][21][22][23][24] copper, [25][26][27] cerium [28][29][30] and iron-based 31,32 oxides due to their strong oxidation ability. Among these transition metal oxides, there are various manganese oxides with different oxidation states, such as MnO 2 , Mn 2 O 3 , Mn 3 O 4 , etc., because of the valence electronic structure of Mn (3d 5 4s 2 ), which exhibit excellent catalytic performance in the removal of atmospheric pollutions (CO, NO x and VOCs).…”

Section: Introductionmentioning

confidence: 99%

Excellent oxidation activity of toluene over core–shell structure Mn₂O₃@MnO₂: role of surface lattice oxygen and Mn species

Zhang

Wang

et al. 2021

J of Chemical Tech & Biotech

View full text Add to dashboard Cite

BACKGROUND Core–shell structure Mn2O3@MnO2 (MnOx) has been prepared using KMnO4 modifying spherical Mn2O3 assembled by nanoparticles, and applied for catalytic toluene oxidation. RESULTS The MnOx sample calcined at 350 °C (MnOx‐1) exhibited much higher catalytic activity compared with Mn2O3 and MnOx‐2 (calcined at 450 °C), good activity stability with recyclability. Bulk structure, redox ability and surface properties were characterized using various techniques. The relationship between the catalytic activity and the surface Mn and oxygen species of these catalysts is discussed in terms of these characterizations. Especially, in situ diffuse reflectance infrared Fourier transform spectroscopic measurements were used to analyze in detail the role of the surface lattice oxygen in the enhanced catalytic performance of MnOx‐1. CONCLUSIONS The excellent activity of the MnOx‐1 catalyst can be attributed to the more surface Mn4+ and many surface lattice oxygen species derived from the special core–shell structure, improving the oxidation of toluene. © 2021 Society of Chemical Industry (SCI).

show abstract

Construction of defective cobalt oxide for methane combustion by oxygen vacancy engineering

Abstract: Defects is pivotal to endow metal oxide catalyst an efficient catalytic oxidation ability. Here, a defects engineering strategy is developed by hand-milling Co3O4 with the aid of Na at room...

Cited by 10 publications

References 43 publications

Co³⁺–O Bond Elongation Unlocks Co₃O₄ for Methane Activation under Ambient Conditions

Co³⁺–O Bond Elongation Unlocks Co₃O₄ for Methane Activation under Ambient Conditions

Recent progress of catalytic methane combustion over transition metal oxide catalysts

Excellent oxidation activity of toluene over core–shell structure Mn₂O₃@MnO₂: role of surface lattice oxygen and Mn species

Contact Info

Product

Resources

About

Construction of defective cobalt oxide for methane combustion by oxygen vacancy engineering

Abstract: Defects is pivotal to endow metal oxide catalyst an efficient catalytic oxidation ability. Here, a defects engineering strategy is developed by hand-milling Co3O4 with the aid of Na at room...

Cited by 10 publications

References 43 publications

Co3+–O Bond Elongation Unlocks Co3O4 for Methane Activation under Ambient Conditions

Co3+–O Bond Elongation Unlocks Co3O4 for Methane Activation under Ambient Conditions

Recent progress of catalytic methane combustion over transition metal oxide catalysts

Excellent oxidation activity of toluene over core–shell structure Mn2O3@MnO2: role of surface lattice oxygen and Mn species

Contact Info

Product

Resources

About

Co³⁺–O Bond Elongation Unlocks Co₃O₄ for Methane Activation under Ambient Conditions

Co³⁺–O Bond Elongation Unlocks Co₃O₄ for Methane Activation under Ambient Conditions

Excellent oxidation activity of toluene over core–shell structure Mn₂O₃@MnO₂: role of surface lattice oxygen and Mn species