Tin and iron co-doping strategy for developing active and stable oxygen reduction catalysts from SrCoO3−δ for operating below 800 °C

Chen, Yubo; Qian, Baoming; Shao, Zongping

doi:10.1016/j.jpowsour.2015.06.095

Cited by 29 publications

(16 citation statements)

References 47 publications

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“…A perovskite catalyst is well known to have lattice oxygen species, especially with the substitution of other elements. [46][47][48] It can be seen that two main peaks are observed with the substitution of Ce for La in the perovskite structure while only one peak is observed for pure LNCO perovskite. The first peak observed at a binding energy of 528-529 eV is attributed to the oxygen ions in the crystal lattice (O 2− ), while the second peak at a binding energy of 530.6-531.2 eV is attributed to adsorbed oxygen species.…”

Section: Reduction Profile (Tpr) Of Fresh Catalystsmentioning

confidence: 98%

Sulfur resistant La_xCe_1−xNi_0.5Cu_0.5O₃ catalysts for an ultra-high temperature water gas shift reaction

Oemar

Bian

Hidajat

et al. 2016

Catal. Sci. Technol.

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A series of La x Ce 1−x Ni 0.5 Cu 0.5 O 3 catalysts was synthesized to study the effect of Ce substitution for La. XRD results show that only a small amount of Ce (10%) is allowable to substitute La to maintain the perovskite structure. The La 0.9 Ce 0.1 Ni 0.5 Cu 0.5 O 3 catalyst has the smallest metal particle size and the highest oxygen mobility among all tested catalysts as observed from the XRD, TPD-O 2 , and XPS results of reduced catalysts. These two factors are very important in achieving the highest catalytic activity of the La 0.9 Ce 0.1 Ni 0.5 Cu 0.5 O 3 catalyst in a water gas shift reaction at 450-650°C. In the presence of H 2 S, the catalytic activity at lower temperature was suppressed due to the formation of stable SO 4 2− species on the metal. However, since the amounts of surface oxygen species and adsorbed H 2 S are much lower at high temperature, the formation of SO 4 2− species is not observed, resulting in higher catalytic activity. The presence of H 2 S at high temperature enhances the formation of formate species, which can decompose to produce methane as the side product of the water gas shift reaction. IntroductionThe Water Gas Shift (WGS) reaction is one of the key reactions for hydrogen production in industry. The reaction is favorable at a low reaction temperature due to exothermicity. However, the reaction rate is lower at lower temperatures. Hence, the WGS reaction is industrially performed in two stages, i.e. high temperature WGS at 350-450°C to increase the reaction rate using an Fe-Cr catalyst, followed by low temperature WGS at 200-250°C to convert the remaining CO in the system using a Cu-Zn catalyst. With current growing interest in hydrogen production via biomass gasification technology which produces sulfur containing syngas, it is important to develop a new catalyst having high activity and stability not only at low (200-250°C) and high temperature (350-450°C) WGS reactions but also at ultra high temperatures (500-650°C) in the presence of a wide range of sulfur concentration. It is understood that biomass gasification is usually performed at high temperatures of 700-900°C. The syngas produced from the biomass gasification has a temperature of 700°C while the conventional WGS reaction requires lower reaction temperatures (200-450°C ). Hence, the syngas needs cooling for the reaction to take place, which means energy loss. The ultra high temperature WGS reaction can minimize the energy loss due to cooling of syngas. The consequences of having a sulphur resistant WGS catalyst is that the downstream hydrogen separation process should have sulphur resistant properties as well. Hence, there is growing interest in sulphur resistant H 2 separation membranes. 1 Various types of sulfur-resistant catalysts have been reported in the literature, such as W-based catalysts, 2,3 Mobased catalysts 4-7 lanthanide oxysulfide La 2 O 2 S, 8,9 noble metal catalysts (Rh,10,(11)(12)(13)), and phosphide catalysts. 14 Sulphided CoMo catalysts in promoted and unpromoted systems have been extensively...

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Section: Reduction Profile (Tpr) Of Fresh Catalystsmentioning

confidence: 98%

Sulfur resistant La_xCe_1−xNi_0.5Cu_0.5O₃ catalysts for an ultra-high temperature water gas shift reaction

Oemar

Bian

Hidajat

et al. 2016

Catal. Sci. Technol.

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“…Co‐doping is extensively used in solid‐state ionics, which can create a combined effect that is unlikely to be realized by single atom doping . In this work, we reported the adoption of a co‐doping strategy to simultaneously realize improved capacity, cycling stability, and voltage maintenance of LRO.…”

Section: Introductionmentioning

confidence: 99%

“…Co-doping is extensively used in solid-state ionics, which can create a combined effect that is unlikely to be realized by single atom doping. [43][44][45] In this work, we reported the adoption of a co-doping strategy to simultaneously realize improved capacity, cycling stability, and voltage maintenance of LRO. Here, Cr and Na were selected as the dopants, since we previously demonstrated that both individually showed excellent performance improvement for the Ru-based LRLO cathodes.…”

Section: Introductionmentioning

confidence: 99%

A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance

et al. 2019

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Summary Lithium‐rich layered oxides (LRLOs) are highly attractive cathode materials for next‐generation lithium‐ion batteries because of their high reversible capacity, but poor cycle performance and voltage decay are two main problems that strongly limit their practical applications. These challenges also apply to the Ru‐based LRLOs of Li2RuO3. The Li2RuO3 cathode material is highly attractive because of their high conductivity and favourable electrochemical reaction kinetics. To overcome the problems associated with Li2RuO3, in contrast to normal single atom doping, here, we propose a Na, Cr co‐doping strategy with the design of Li2−xNaxRu0.95Cr0.05O3 (x = 0, 0.02, 0.06, and 0.1) series materials. Cr doping increases capacity, and Na doping suppresses voltage decay. As a result, the discharge capacity of the optimal Li1.98Na0.02Ru0.95Cr0.05O3 sample over 240 mAh/g after 50 charge‐discharge cycles at 0.2 C is maintained, and the capacity retention reaches a value of 80.5% compared with 69.1% for the undoped Li2RuO3. The value of the voltage decay in the Li1.98Na0.02Ru0.95Cr0.05O3 sample is 125 mV after 100 cycles at a rate of 1 C, and the voltage decay is 188.4 mV for the undoped Li2RuO3. This finding will expand the scope for designing novel layered electrodes with excellent performance.

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“…These cells are known as intermediate temperature SOFCs (IT-SOFCs). [6][7][8][9][10][11][12] High MIECs can extend the ORR active sites to the entire cathode surface, significantly improving the catalytic activity of the cathode materials at reduced temperature. [3][4] However, sluggish oxygen reduction reaction (ORR) kinetics of the cathode in the IT range severely decreases power density.…”

Section: Introductionmentioning

confidence: 99%

Unveiling Lithium Roles in Cobalt‐Free Cathodes for Efficient Oxygen Reduction Reaction below 600 °C

Rehman

Knibbe

et al. 2019

ChemElectroChem

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Improving the sluggish electrocatalytic oxygen reduction reaction (ORR) over cobalt-free cathodes at 550-800°C is imperative to circumvent challenges faced by practical operation of intermediate temperature solid oxide fuel cells. In this work, we synthesize novel cobalt-free, lithium (Li)-doped, perovskite oxides Sr 1-x Li x Fe 0.8 Nb 0.1 Ta 0.1 O 3-δ (SLFNTx, x = 0-0.1) as cathodes for efficient ORR catalysis. When the Li concentration is less than 0.05, ORR activity is enhanced by over 1.6-fold in comparison to the undoped SFNT below 600°C in both symmetrical and anode-supported single cells configurations. Our comprehensive investigation over crystal structure, surface, and mixed conductivities revealed that a moderate concentration (< 0.05) of Li could bestow the perovskite with a stable cubic perovskite structure that contains an optimal concentration of oxygen vacancies and A-site deficiencies. Such trend originates from the lower electronegativity and smaller size of Li dopant than the strontium host. The lower electronegativity increases oxygen vacancies. The small Li dopant induces thermal-migration of Li species and creates A-site deficiency. These insights highlight an effective strategy to advance the performance of cobalt-free ORR electrocatalyst below 600°C through in situ thermal surface migration of the A-site cations.

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Tin and iron co-doping strategy for developing active and stable oxygen reduction catalysts from SrCoO3−δ for operating below 800 °C

Cited by 29 publications

References 47 publications

Sulfur resistant La_xCe_1−xNi_0.5Cu_0.5O₃ catalysts for an ultra-high temperature water gas shift reaction

Sulfur resistant La_xCe_1−xNi_0.5Cu_0.5O₃ catalysts for an ultra-high temperature water gas shift reaction

A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance

Unveiling Lithium Roles in Cobalt‐Free Cathodes for Efficient Oxygen Reduction Reaction below 600 °C

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Tin and iron co-doping strategy for developing active and stable oxygen reduction catalysts from SrCoO3−δ for operating below 800 °C

Cited by 29 publications

References 47 publications

Sulfur resistant LaxCe1−xNi0.5Cu0.5O3 catalysts for an ultra-high temperature water gas shift reaction

Sulfur resistant LaxCe1−xNi0.5Cu0.5O3 catalysts for an ultra-high temperature water gas shift reaction

A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance

Unveiling Lithium Roles in Cobalt‐Free Cathodes for Efficient Oxygen Reduction Reaction below 600 °C

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Sulfur resistant La_xCe_1−xNi_0.5Cu_0.5O₃ catalysts for an ultra-high temperature water gas shift reaction

Sulfur resistant La_xCe_1−xNi_0.5Cu_0.5O₃ catalysts for an ultra-high temperature water gas shift reaction