MOLECULES
·
2023
·Vol. 28
·期 14
·5296
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IF 4.6
Zhenjiang Lu,Wenjin Qin,Juan Ma,Yali Cao,Shujuan Bao
Direct formic acid fuel cells (DFAFCs) are one of the most promising power sources due to its high conversion efficiency; relatively low carbon emissions, toxicity, and flammability; convenience; and low-cost storage and transportation. However, the key challenge to large-scale commercial applications is its poor power performance and the catalyst’s high preparation cost. In this study, a new sandwich-structured Pd/polypyrrole-graphene/Pd (Pd/PPy-Gns/Pd)-modified glassy carbon electrode (GCE) was prepared using a simple constant potential (CP) electrodeposition technique. On the basis of the unique synthetic procedure and structural advantages, the Pd/PPy-Gns/Pd shows a fast charge/mass transport rate, high electrocatalytic activity, and great stability for formic acid electro-oxidation (FAO). The mass activity of Pd/PPy-Gns/Pd electrode reaches 917 mA·mg−1Pd. The excellent catalytic activity is mainly due to the uniform embedding of Pd nanoparticles on the polypyrrole-graphene (PPy-Gns) support, which exposes more active sites, and prevents the shedding and inactivation of Pd nanoparticles. At the same time, the introduction of graphene (Gns) in the PPy further improved the conductivity of the catalyst and accelerated the transfer of electrons.Keywords:electrodeposition;polypyrrole;Pd nanoparticles;DFAFCs
研究领域:
电化学
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材料科学
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能源技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Huiling Li,Jingkun Yu,Weibin Wang,Juan Ding,Yongming Sui
Direct formic acid fuel cells (DFAFCs) are considered promising power sources for next-generation portable electronic devices due to their high theoretical energy density, excellent storage stability, and low fuel permeability. However, the multistep nature of the formic acid oxidation (FAO) pathway increases the complexity of designing efficient anode catalysts, posing a significant challenge to the commercialization of DFAFCs. Here, we present a unique example of significantly enhancing the catalytic performance of Pd-based catalysts for FAO through facet effect-regulated nitrogen occupation. Our approach involves the synthesis of nitrogen-doped Pd nanocubes (NCs) and cuboctahedrons (COs). Theoretical and experimental analyses reveal that the subsurface octahedral (O) site N occupation on the (100) facet reduces the energy barrier for the complete FAO process, thereby significantly enhancing the catalytic activity of PdN NCs. In contrast, the tetrahedral (T) site N occupation on the (111) facet increases the adsorption free energy difference between *HCOO and *COOH, which reduces the accumulation of CO and endows PdN COs with superior catalytic stability. This study provides valuable insights for the design of advanced anode catalysts in DFAFCs.
研究领域:
能源材料
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电化学
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催化化学
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产品关联
DOI
PubMed
高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Qizhi Dong,Tianwu Yin,Hansheng Wan,Guiming Zhu,Gang Yu,Cancheng Guo
Based on electrostatic self-assembly technology, Pd electrocatalyst with high efficiency and excellent CO-tolerance, which is supported on TiO 2 surface modified by amino-rich, cationic poly (diallyldimethylammonium chloride) (PDDA), was prepared. Through electrostatic interaction, Pd precursors were uniformly distributed on TiO 2 (P) and then in situ reduced into Pd nanoparticles (NPs). in such process, PDDA produced a large number of amine to facilitate the uniform distribution of Pd NPs on the surface of TiO 2 . After that，Pd/TiO 2 (P) was mixed with carbon black as anodic catalysts for formic acid oxidation reaction. Transmission electron microscope images and X-ray diffraction patterns revealed that Pd NPs with an average size of ∼3 nm were uniformly dispersed on TiO 2 . Moreover, with the application of cyclovoltammetry and chronoamperometry, we demonstrated the significant enhancement in the electrocatalytic activity and the tolerance toward CO poisoning when compared with Pd/TiO 2 -C for direct formic acid fuel cells.
研究领域:
材料科学
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电化学
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能源科学
✓ 已验证
DOI
高影响因子
Advanced Sustainable Systems
·
2020
·Vol. 4
·期 7
·2000065
·
IF 4.869
Wenrui Yan,Yan Xiang,Jin Zhang,Shanfu Lu,San Ping Jiang
Development of direct formic acid fuel cell (DFAFC) is significantly constrained by low output performance and poor durability because of the sluggish formic acid oxidation reaction (FAOR) and the poisoning by CO ads intermediate on the Pt-based electrocatalyst at low operating temperatures. By operating DFAFCs at elevated temperatures, the peak power density (PPD) of the cell based on the Pt/C catalyst increases significantly. For example, the PPD of DFAFC reaches 198 mW cm −2 at 240 °C, eight times higher than that of the DFAFC at 70 °C. The study shows the surprising transition in power performance of DFAFCs at elevated temperatures. The increase of PPD for DFAFC against temperature is 121 mW cm −2 /100 °C at temperatures above 115 °C, almost three times higher than the 45 mW cm −2 /100 °C obtained at lower temperatures. The fundamental reason for the substantially enhanced power output and durability is the gradual transformation of the reaction kinetics from sluggish direct FAOR at low temperatures to fast H 2 oxidation reaction at elevated temperatures due to the increased in situ decomposition of formic acid on Pt/C catalysts at temperatures above 100 °C. This study demonstrates that operation at temperatures above 160 °C is most effective to promote performance and durability of DFAFCs.
研究领域:
能源科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2023
·
IF 13.1
Zhongying Fang,Ziwei Zhang,Shemsu Ligani Fereja,Jinhan Guo,Xinjie Tong,Yue Zheng,Rupeng Liu,Xiaolong Liang,Leting Zhang,Zongjun Li,Wei Chen
Direct formic acid fuel cell (DFAFC) is an important research project in clean energy field. However, commercialization of DFAFC is still largely limited by the available catalysts with unsatisfied activity, durability and cost for formic acid electrooxidation (FAEO). Using Pt- and Pd-based nanoclusters as electrocatalysts is a particularly promising strategy to solve the above problem, but two attendant problems need to be solved firstly. (I) The controllable synthesis of practicable and stable sub-2 nm clusters remains challenging. (II) The catalyzing mechanism of sub-2 nm metal clusters for FAEO has not yet completely understood. Herein, different from traditional solution synthesis, by designing a novel supporting material containing electron-rich and electron-deficient functional groups, size- and dispersion-controllable synthesis of ∼1 nm PtPd nanoclusters is realized by an electrochemical process. The electrocatalytic properties and reaction mechanism of the PtPd nanoclusters for the FAEO were studied by different electrochemical techniques, in-situ fourier transform infrared (FTIR) spectra and density functional theory (DFT) calculations. The tiny PtPd nanoclusters have much higher catalytic activity and durability than commercial Pt/C, Pd/C and 3.5 nm PtPd nanoparticles. The present study shows that the metal-reactant interaction plays a decisive role in determining the catalytic activity and cluster-support interaction plays a decisive role in enhancing the durability of electrocatalyst. The ratio and arrangement of Pt and Pd atoms on the surface of 1 nm PtPd cluster as well as the overall valence state, d-band center and specific surface area make them exhibit different catalytic performance and reaction mechanism from nanoparticle catalysts. In addition, in situ FTIR and DFT calculations showed that on the surface of PtPd clusters, the generation of CO 2 through trans-COOH intermediate is the most optimal reaction pathway for the FAEO.
研究领域:
材料科学
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能源化学
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电催化
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2021
·Vol. 168
·期 6
·064519
·
IF 4.316
Bowei Pan,Fuyi Chen,Junpeng Wang,Quan Tang,Longfei Guo,Tao Jin,Chenxi Peng,Liang An,Yu Chen
A passive air-breathing formate fuel cell with PdAuAg alloy nanoparticles supported on the carbon nanotube (CNT) pasted on nickel foam (NF) as anode is reported in this work. With optimization, a maximum power density of 16 mW cm−2 with PdAuAg/CNT on NF as anode is achieved, which is 2.2 time of that achieved by using commercial Pd/C on NF (7.3 mW cm−2). Furthermore, the cell with PdAuAg/CNT on NF as anode can steadily discharge at 5 mA cm−2 for more than 28 h continuously. This is, to our knowledge, the best performance of passive air-breathing formate fuel cells reported so far and PdAuAg/CNT on NF as anode can be considered as the state-of-the-art for the passive air-breathing formate fuel cell. These results suggested that the PdAuAg/CNT catalyst probably provides an alternative avenue for developing the anode electrocatalysts for passive air-breathing formate fuel cell applications.
研究领域:
材料科学
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能源技术
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催化化学
✓ 已验证
DOI
高影响因子
CHEMISTRY LETTERS
·
2016
·Vol. 45
·期 7
·732-734
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IF 1.55
Liu Xinyue,Dai Changqing,Wu Dengfeng,Fisher Adrian,Liu Zhiping,Cheng Daojian
PdAg bimetallic and PdAgCo trimetallic nanoparticles (NPs) are synthesized by a one-pot method in an organic solvent medium. Our results show that the catalytic activity of PdAgCo/C (1133.249 mA mgPd−1) for formic acid oxidation (FAO) is ca. 2.4 times larger than commercial Pd/C (483.563 mA mgPd−1) and 1.7 times larger than PdAg/C (680.741 mA mgPd−1). This study indicates that Co doping in PdAg bimetallic NPs can significantly improve its FAO activity. It is expected that the as-synthesized PdAgCo trimetallic NPs could be used as high-performance catalysts for direct formic acid fuel cells (DFAFCs).
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2025
·
IF 5.5
Yixin Xu,Yiping Wang,Ying Li,Na Su,Shuozhen Hu,Xinsheng Zhang
Direct formic acid fuel cells (DFAFCs) are promising portable power sources with the advantages of easy handling and high theoretical open-circuit voltage. Exploring efficient Pd-based catalysts for formic acid oxidation (FAO) on the anode is important for the widespread use of DFAFCs. However, formic acid decomposition on the Pd surface restricts the FAO activity of the catalyst, in which the adsorbed hydrogen atoms combine together to form hydrogen molecules instead of generating H+ ions and transferring electrons at the interface. Herein, we report a polarization-induced electric field (PEF) strategy to facilitate FAO on Pd by directing interfacial charge transfer. Pd/TBT-X@SC catalysts with PEF are synthesized with tetragonal phase barium titanate (TBT) as the core, carbonized sucrose as the shell, and palladium nanoparticles as the active sites. The PEF strength is successfully regulated by varying the particle size of TBT. Stronger PEF and proper carbonized sucrose thickness facilitate the interfacial charge transfer on the Pd surface, thereby promoting the electrooxidation of adsorbed hydrogen to H+ ions and converting CO-like species to CO2. Moreover, PEF also induces the formation of electron-deficient Pd, thus reducing the bond strength between Pd and adsorbed intermediate species such as H and CO-like species. Consequently, FAO selectivity, activity, and anti-CO-like poisoning species property of Pd are enhanced by the introduction of PEF. Among all the catalysts, Pd/TBT-100 nm@SC exhibits the highest catalytic activity (7.49 mA·cm–2) and resistance to CO-like poisoning species. This work offers a new strategy for the design of catalysts with high FAO selectivity.
研究领域:
材料科学
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电化学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2020
·Vol. 12
·期 5
·3469-3481
·
IF 6.895
Longfei Guo,Fuyi Chen,Tao Jin,Huazhen Liu,Nan Zhang,Yachao Jin,Qiao Wang,Quan Tang,Bowei Pan
Formate is a kind of carbon-neutral fuel that can be synthesized by electrochemical conversion of CO2, however, the generated aqueous formate electrolyte is still short of potential application. Here, formate solution is proposed to be utilized as anode fuels of direct formate fuel cells through the formate oxidation reaction (FOR), and graphene supported AgPd nanoalloys (AgPd/rGO) are prepared to catalyze the FOR. Specifically, the mass activity of the as-prepared Ag49Pd51/rGO catalyst is 4.21 A mg−1Pd and the retention activity of Ag49Pd51/rGO is 49.1% of initial activity after successive 500 cycles, which is 2.48 and 3.03 times higher than that of unsupported Ag51Pd49 nanoalloys. When increasing the positive scan limit from 0.0 to 0.8 V, the mass activity of the Ag49Pd51/rGO catalyst increases from 2.32 to 6.03 A mg−1Pd and Pd surface coverage increases from 51.87% to 62.42%, indicating the occurrence of surface reconstruction where Pd atoms migrate to the surface of AgPd nanoalloys, and less intensive reconstruction is observed in unsupported Ag51Pd49 nanoalloys, whose mass activity increases from 1.35 to 2.49 A mg−1Pd. The driving force and kinetic path are calculated for the surface reconstruction induced by the adsorption of H, O and C atoms, in the case of C atoms on graphene, the segregation energy of surface Pd atoms in the AgPd nanoalloy is −1.16 eV, and the activation energy for the migration of subsurface Pd atoms to the surface is 0.54 eV, which are lower than the segregation (0.03 eV) and activation (2.06 eV) energy on a clean alloy surface.
研究领域:
材料科学
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电化学
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催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2019
·
IF 7.467
Fumin Li,Qi Xue,Ge Ma,Shuni Li,Mancheng Hu,Hongchang Yao,Xin Wang,Yu Chen
Inhibiting formic acid decomposition on Pd-based electrocatalysts is a major challenge for realizing the commercialization of direct formic acid fuel cells (DFAFCs). Inspired by the catalytic characteristics of formic acid decomposition/electrooxidation on Pd-based materials, here we synthesize intermetallic bimetallic Pd–Sn nanonetworks (NNWs) to deal with this problem. Compared to commercial Pd black with high catalytic activity , the strong Pd–Sn electronic interaction in intermetallic Pd 3 Sn 2 NNWs induces the complete inhibition of formic acid decomposition at 80 °C. Parallelly, Pd 3 Sn 2 NNWs exhibit mass activity of 448 A g Pd −1 for formic acid electrooxidation due to Pd–Sn synergistic effect , which is 2.1 times higher than that of commercial Pd black. The stable intermetallic structure and three-dimensionally interconnected architecture endow Pd 3 Sn 2 NNWs with better electrochemical and electrocatalytic durability, suggesting promising cost-effective anode catalysts for DFAFCs.
研究领域:
材料科学
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电化学
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2022
·Vol. 10
·期 46
·24701-24707
·
IF 14.511
Yu-Chuan Jiang,Yu Ding,Fu-Min Li,Shi-Bin Yin,Dong-Sheng Li,Xi-Fei Li,Yu Chen
The intrinsically sluggish kinetics of Pt towards the formate oxidation reaction (FOR) severely impedes its application in direct formate fuel cells (DFFCs). This study reports the synthesis of ultrafine Pd@PdPt nanowires (NWs) with a Pd–Pt single-atom alloy shell via an atomic galvanic displacement reaction. Pd@PdPt0.024 NWs with optimized composition exhibit a remarkable promoted specific activity of 98.2 A m−2 at 0.59 V towards the FOR, which is a 6.5- and 117.7-fold activity enhancement compared to original Pd NWs and commercial Pt catalysts. Density functional theory (DFT) calculations reveal that the electronic interaction between Pd and Pt as well as the modified Pt coordination environment endow the atomically dispersed Pt active site with an altered d-band structure and unique adsorption properties with a broken scaling relationship. The development of Pd@PdPt0.024 NWs will stimulate deeper insight into the FOR mechanism on Pt and hold promise for practical applications in DFFCs.
研究领域:
材料科学
·
催化化学
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能源科学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2019
·
IF 4.084
Xianda Sun,Yinshi Li
The disadvantage of anion ionomer that possesses low hydroxide conductivity, and thermal and chemical instability hinders the development of the high-performance anion-exchange membrane direct liquid fuel cells. Instead of adding additional base and synthesizing high-conductivity ionomer material, by gaining insight into species transports, herein, we propose an anion-ionomer-free anion-exchange membrane direct formate fuel cell (AEM DFFC). Experimental result reveals that this conceptual anion-ionomer-free AEM DFFC can operate stably within a 6-h constant-current discharge at 10 mA cm −2 , mainly because formate hydrolysis renders a high OH − conductivity. It was also found that the anion-ionomer-free AEM DFFC yields a peak power density as high as 41 mW cm −2 at 40 °C, 40% higher than that of the conventional quaternary ammonia polysulfone anion-ionomer AEM DFFC. This can be attributed to the fact that the OH − -containing formate solution facilitates the mass and charge transports, thereby enlarging the triple-phase boundary for both anodic formate oxidation reaction and cathodic oxygen reduction reaction .
研究领域:
能源科学
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材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）