原子精确的(AgPd)_(27)团簇用于硝酸盐电还原制氨:一种配体诱导策略来调控金属核  

Atomically Precise(AgPd)_(27) Nanoclusters for Nitrate Electroreduction to NH_(3):Modulating the Metal Core by a Ligand Induced Strategy

作　　者：秦露冰 孙芳 李美银 范浩 王立开 唐青 王春栋[4] 唐正华 Lubing Qin;Fang Sun;Meiyin Li;Hao Fan;Likai Wang;Qing Tang;Chundong Wang;Zhenghua Tang(New Energy Research Institute,School of Environment and Energy,South China University of Technology,Guangzhou 510006,China;School of Chemistry and Chemical Engineering,Chongqing Key Laboratory of Theoretical and Computational Chemistry,Chongqing University,Chongqing 401331,China;School of Chemistry and Chemical Engineering,Shandong University of Technology,Zibo 255049,Shandong Province,China;School of Integrated Circuits,Wuhan National Laboratory for Optoelectronics,Huazhong University of Science and Technology,Wuhan 430074,China;Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education,Harbin 150001,China.)

机构地区：[1]华南理工大学环境与能源学院新能源研究所,广州510006 [2]重庆大学化学化工学院重庆市理论与计算化学重点实验室,重庆401331 [3]山东理工大学化学与化工学院,山东淄博255049 [4]华中科技大学集成电路学院武汉光电子国家实验室,武汉430074 [5]黑龙江大学功能无机材料化学教育部重点实验,哈尔滨150001

出　　处：《物理化学学报》2025年第1期97-110,共14页Acta Physico-Chimica Sinica

基　　金：功能无机材料化学教育部重点实验室(黑龙江大学)开放基金资助;广东省自然科学基金(2023A0505050107)的资助(Z.T.);重庆市科学技术委员会(cstc2020jcyj-msxmX0382)的支持(Q.T.)。

摘　　要：电化学硝酸根还原反应(eNO_(3)^(–)RR)合成氨是一种可持续的将环境污染物转化为高附加值产品的方法。钯基双金属纳米催化剂作为高效催化剂已显示出巨大的前景,但调控其组成和构型以提高催化性能并实现深入的机理理解仍然很有挑战。通过使用不同供/吸电子官能团的两个配体,我们成功地制备了两个原子精确的(AgPd)27双金属团簇,即Ag_(18)Pd_(9)(C_(8)H_(4)F)_(24)(简称Ag_(18)Pd_(9))和Ag_(22)Pd_(5)(C_(9)H_(10)O_(2))_(26)(简称Ag_(22)Pd_(5))。两个团簇的金属核具有明显不同组成和构型,其中Ag_(18)Pd_(9)为中间层是9个Pd原子的“三明治”型金属核结构,Ag_(22)Pd_(5)为M_(13)构型组成的棒状金属核结构,而5个钯原子位于M_(13)构型的顶点和中心位置。出乎意料的是,Ag_(22)Pd_(5)表现出明显优于Ag_(18)Pd_(9)的eNO_(3)^(−)RR性能。具体表现来说,Ag_(22)Pd_(5)在−0.6 V时NH_(3)的法拉第效率和产生速率达到最高,分别为94.42%和1.41 mmol·h^(−1)·mg^(−1),但Ag_(18)Pd_(9)的NH_(3)的最高法拉第效率和产生速率只有在−0.5 V时的43.86%和0.41 mmol·h^(−1)·mg^(−1)。原位衰减全反射表面增强红外光谱(ATR-SEIRAS)测试提供了反应中间体的实验证据,从而揭示了反应途径,也表明Ag_(22)Pd_(5)比Ag_(18)Pd_(9)具有更强的NO_(3)–吸附和NH_(3)脱附能力。理论计算表明,配体脱落的团簇可以暴露AgPd双金属位点,Ag-Pd位点为协同催化活性位点,不同构型的AgPd活性位点有显著差异,其中Ag_(22)Pd_(5)中的活性位点更有利于NO_(3)^(−)吸附和NH_(3)脱附,从而加速催化过程。Electrochemical nitrate reduction reaction(eNO_(3)^(–)RR)to synthesize NH_(3)is a sustainable method to convert environmental contaminants into valuables.Pd based bimetallic nanocatalysts have demonstrated great promise as efficient catalysts,yet modulating the composition and configuration to improve the catalytic performance and achieve comprehensive mechanistic understanding remains challenging.Herein,by employing two ligands with different electron functional groups,we successfully prepared two atomically precise(AgPd)27 bimetallic clusters of Ag_(18)Pd_(9)(C_(8)H_(4)F)_(24)(Ag_(18)Pd_(9))and Ag_(22)Pd_(5)(C_(9)H_(10)O_(2))_(26)(Ag_(22)Pd_(5)).The two clusters possess markedly different metal core composition and configuration,where Ag_(18)Pd_(9)has a sandwich metal core structure with 9 Pd atoms located in the middle layer and Ag_(22)Pd_(5)has a rodshaped metal core structure composed of the M_(13)configuration with 5 Pd atoms located at the center and vertices of the M_(13)configuration.Unexpectedly,Ag_(22)Pd_(5)exhibited remarkably superior eNO_(3)^(−)RR performance than Ag_(18)Pd_(9).Specifically,the highest Faradaic efficiency of NH_(3)(FENH_(3))and its yield rate can reach 94.42%and 1.41 mmol∙h^(−1)∙mg^(−1)at−0.6 V vs.RHE for Ag_(22)Pd_(5),but the largest FENH_(3)and NH_(3)yield rate is only 43.86%and 0.41 mmol∙h^(−1)∙mg^(−1)at−0.5 V vs.RHE for Ag_(18)Pd_(9).The in situ attenuated total reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS)test provides the experimental evidence of the reaction intermediates hence revealing the reaction pathway,also shows that Ag_(22)Pd_(5)has stronger capability for NO_(3)^(−)adsorption and NH_(3)desorption than that of Ag_(18)Pd_(9).Theoretical calculations indicate that the de-ligated clusters can expose the available AgPd bimetallic sites,synergistically serving as effective active sites and the different configurations result in significantly different catalytic activities,where the active sites in Ag_(22)Pd_(5)are more f

关 键 词：电化学硝酸盐还原反应 原子精确双金属团簇 Ag_(18)Pd_(9)(C_(8)H_(4)F)_(24) Ag_(22)Pd_(5)(C_(9)H_(10)O_(2))_(26) 原位衰减全反射表面增强红外光谱 理论计算 

分 类 号：O646[理学—物理化学]