电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍...电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍铁羟基/氢氧化物(NiFe(oxy)hydroxides)是近期研究的热点,其在碱性条件下具有极低的OER过电位,部分材料性能甚至超过了贵金属基催化剂,如IrO_(2)和RuO_(2).然而,NiFe(oxy)hydroxides的长期催化稳定性,尤其是在大电流下的长期催化稳定性,成为限制其实际应用的主要问题,这主要是由于铁元素的严重流失导致的.因此,如何有效控制和利用电化学溶解/沉积动力学成为稳定铁位点的关键.为克服该挑战,本文提出了一种大电流极化重构方法来固定活性铁位点.通过在大电流(1.5 A cm^(-2))下对材料进行表面快速极化重构,成功制备了FeOOH@NiOOH(eFNO_(L))电催化剂.eFNO_(L)不仅具有稳定的铁位点,还暴露出高指数晶面,因此eFNO_(L)同时展现出较好的OER催化活性和稳定性.同时,密度泛函理论计算结果表明,与具有低指数晶面的FeNiOOH相比,大电流极化工程制备的分相eFNO_(L)对铁位点表现出更高的结合能,可以有效抑制OER过程中的铁流失,且高指数晶面在改变速率决定步骤和减少吸附能垒上具有更大的优势.电化学测试结果表明,经过优化后的eFNO_(L)催化剂在产生100和500 mA cm^(-2)大电流密度仅需234和27 mV的过电位,并且具有较小的Tafel斜率(35.2 mV dec^(-1)).由于铁位点结合能的提高,eFNO_(L)催化剂在500 mA cm^(-2)的电流密度下能够稳定催化超过100 h,且仅有1.5%的性能衰减,优于近期报道的大多数镍铁基OER催化剂.综上,本文为开发高活性和高稳定性能的催化剂提供了一种有效的大电流电化学重构策略,在电解水制氢领域实现其工业化的大规模应用方面显示出巨大潜力,有望降低可持续电解水制氢成本.展开更多
Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells.However...Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells.However,their widespread commercial applications are limited by complicated synthetic procedures for mass production.Herein,we are proposing a simple,green mechanochemical approach to synthesize zeolitic imidazolate frameworks precursors for the production of atomically dispersed“Fe-N_(4)”sites in holey carbon nanosheets on a large scale.The thin porous carbon nanosheets(PCNs)with atomically dispersed“Fe-N_(4)”moieties can be prepared in hectogram scale by directly pyrolysis of salt-sealed Fe-based zeolitic imidazolate framework-8(Fe-ZIF-8@NaCl)precursors.The PCNs possess large specific surface area,abundant lamellar edges and rich“Fe-N_(4)”active sites,and show superior catalytic activity towards oxygen reduction reaction in an acid electrolyte.This work provides a promising approach to cost-effective production of atomically dispersed transition metal catalysts on large scale for practical applications.展开更多
The process of γ(fcc)→γ(fcc)+γ'(L12)phase transformation was simulated by using microscopic phase-field method for the low supersaturation NiAl9Fe6 alloy.It is found that in the γ' phase,the ordering degr...The process of γ(fcc)→γ(fcc)+γ'(L12)phase transformation was simulated by using microscopic phase-field method for the low supersaturation NiAl9Fe6 alloy.It is found that in the γ' phase,the ordering degree of Al atoms is obviously higher than that of Fe atoms,and the ordering of Al atoms precedes their clustering,while the case of Fe atoms is opposite.The α site is mainly occupied by Ni atoms,while the β site is occupied in common by Al,Fe and Ni atoms.At order-disorder interphase boundary,the ordering degree of Al atoms is higher than that of Fe atoms,and at the β site,the Fe atomic site occupation probabilities vary from high to low during ordering;the Al atomic site occupation probabilities are similar to those of Fe atoms,but their values are much higher than those of Fe atoms;Ni atoms are opposite to both of them.Meanwhile,during the ordering transformation,γ' phase is always a complex Ni3(AlFeNi)single-phase,and it is precipitated by the non-classical nucleation and growth style.Finally,in the alloy system,the volume of γ' ordered phase is less than that of γ phase,and the volume ratio of order to disorder is about 77%.展开更多
Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the ac...Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the active site hosts, its hostility to electron/mass transfer could lead to the incomplete fulfillment of the catalytic activity. Besides, the formation of inactive metallic Fe particles during the conventional catalyst synthesis could also decrease the active site density and complicate the identification of real active site. Herein, we developed a facial hydrogen etching methodology to yield single site Fe-N-C catalysts featured with micro/mesoporous hierarchical structure. The hydrogen concentration in pyrolysis process was designated to effectively regulate the pore structure and active site density of the resulted catalysts.The optimized sample achieves excellent ORR catalytic performance with an ultralow H2O2 yield(1%)and superb stability over 10,000 cycles. Our finding provides new thoughts for the rational design of hierarchically porous carbon-based materials and highly promising non-precious metal ORR catalysts.展开更多
文摘电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍铁羟基/氢氧化物(NiFe(oxy)hydroxides)是近期研究的热点,其在碱性条件下具有极低的OER过电位,部分材料性能甚至超过了贵金属基催化剂,如IrO_(2)和RuO_(2).然而,NiFe(oxy)hydroxides的长期催化稳定性,尤其是在大电流下的长期催化稳定性,成为限制其实际应用的主要问题,这主要是由于铁元素的严重流失导致的.因此,如何有效控制和利用电化学溶解/沉积动力学成为稳定铁位点的关键.为克服该挑战,本文提出了一种大电流极化重构方法来固定活性铁位点.通过在大电流(1.5 A cm^(-2))下对材料进行表面快速极化重构,成功制备了FeOOH@NiOOH(eFNO_(L))电催化剂.eFNO_(L)不仅具有稳定的铁位点,还暴露出高指数晶面,因此eFNO_(L)同时展现出较好的OER催化活性和稳定性.同时,密度泛函理论计算结果表明,与具有低指数晶面的FeNiOOH相比,大电流极化工程制备的分相eFNO_(L)对铁位点表现出更高的结合能,可以有效抑制OER过程中的铁流失,且高指数晶面在改变速率决定步骤和减少吸附能垒上具有更大的优势.电化学测试结果表明,经过优化后的eFNO_(L)催化剂在产生100和500 mA cm^(-2)大电流密度仅需234和27 mV的过电位,并且具有较小的Tafel斜率(35.2 mV dec^(-1)).由于铁位点结合能的提高,eFNO_(L)催化剂在500 mA cm^(-2)的电流密度下能够稳定催化超过100 h,且仅有1.5%的性能衰减,优于近期报道的大多数镍铁基OER催化剂.综上,本文为开发高活性和高稳定性能的催化剂提供了一种有效的大电流电化学重构策略,在电解水制氢领域实现其工业化的大规模应用方面显示出巨大潜力,有望降低可持续电解水制氢成本.
基金the National Key Research and Development Program of China(No.2017YFA0206500)the Key Program of National Natural Science Foundation of China(No.51732002)+3 种基金National Natural Science Foundation of China(No.21971002)the Fundamental Research Funds for the Central Universities(Nos.buctrc202118 and buctrc202007)Distinguished Scientist Program at BUCT(No.buctylkxj02)Beijing Advanced Innovation Center for Soft Matter Science and Engineering.
文摘Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells.However,their widespread commercial applications are limited by complicated synthetic procedures for mass production.Herein,we are proposing a simple,green mechanochemical approach to synthesize zeolitic imidazolate frameworks precursors for the production of atomically dispersed“Fe-N_(4)”sites in holey carbon nanosheets on a large scale.The thin porous carbon nanosheets(PCNs)with atomically dispersed“Fe-N_(4)”moieties can be prepared in hectogram scale by directly pyrolysis of salt-sealed Fe-based zeolitic imidazolate framework-8(Fe-ZIF-8@NaCl)precursors.The PCNs possess large specific surface area,abundant lamellar edges and rich“Fe-N_(4)”active sites,and show superior catalytic activity towards oxygen reduction reaction in an acid electrolyte.This work provides a promising approach to cost-effective production of atomically dispersed transition metal catalysts on large scale for practical applications.
基金Project(50671084)supported by the National Natural Science Foundation of ChinaProject(Z200714)supported by Graduate Starting Seed Fund of Northwestern Polythechnical University,China
文摘The process of γ(fcc)→γ(fcc)+γ'(L12)phase transformation was simulated by using microscopic phase-field method for the low supersaturation NiAl9Fe6 alloy.It is found that in the γ' phase,the ordering degree of Al atoms is obviously higher than that of Fe atoms,and the ordering of Al atoms precedes their clustering,while the case of Fe atoms is opposite.The α site is mainly occupied by Ni atoms,while the β site is occupied in common by Al,Fe and Ni atoms.At order-disorder interphase boundary,the ordering degree of Al atoms is higher than that of Fe atoms,and at the β site,the Fe atomic site occupation probabilities vary from high to low during ordering;the Al atomic site occupation probabilities are similar to those of Fe atoms,but their values are much higher than those of Fe atoms;Ni atoms are opposite to both of them.Meanwhile,during the ordering transformation,γ' phase is always a complex Ni3(AlFeNi)single-phase,and it is precipitated by the non-classical nucleation and growth style.Finally,in the alloy system,the volume of γ' ordered phase is less than that of γ phase,and the volume ratio of order to disorder is about 77%.
基金Project (51002128) supported by the National Natural Science Foundation of ChinaProject (2012M511737) supported by the National Science Foundation for Post-Doctor of China
文摘研制高活性的Fe/N/C氧还原催化剂对于降低燃料电池成本、实现商业化应用有重要意义.为实现Fe/N/C催化剂的理性设计,需要深入研究其活性位结构.本文发展一种研究活性位结构的新策略,以预先合成好的聚间苯二胺基Fe/N/C催化剂(Pm PDA-Fe Nx/C)为起始物,对其在1000~1500 o C高温下再次进行热处理并使其失活,通过关联催化剂热处理前后的结构变化与氧还原催化性能来揭示活性位结构.实验结果表明,随着热处理温度升高,活性中心结构被破坏,铁原子析出团聚并形成纳米颗粒,氮元素挥发损失,导致催化剂失活.XPS分析显示,低结合能含氮物种的含量与催化剂的ORR活性呈良好的正相关性,表明活性中心很可能是由吡啶N和Fe-N物种构成的.
基金supported by the National Natural Science Foundation of China(21633008,21433003,U1601211,21733004)National Science and Technology Major Project(2016YFB0101202)+1 种基金Jilin Province Science and Technology Development Program(20150101066JC,20160622037JC,20170203003SF,20170520150JH)Hundred Talents Program of Chinese Academy of Sciences and the Recruitment Program of Foreign Experts(WQ20122200077)
文摘Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the active site hosts, its hostility to electron/mass transfer could lead to the incomplete fulfillment of the catalytic activity. Besides, the formation of inactive metallic Fe particles during the conventional catalyst synthesis could also decrease the active site density and complicate the identification of real active site. Herein, we developed a facial hydrogen etching methodology to yield single site Fe-N-C catalysts featured with micro/mesoporous hierarchical structure. The hydrogen concentration in pyrolysis process was designated to effectively regulate the pore structure and active site density of the resulted catalysts.The optimized sample achieves excellent ORR catalytic performance with an ultralow H2O2 yield(1%)and superb stability over 10,000 cycles. Our finding provides new thoughts for the rational design of hierarchically porous carbon-based materials and highly promising non-precious metal ORR catalysts.
