Element table of TM-substituted polyoxotungstates for direct electrocatalytic reduction of nitric oxide to ammonia: A DFT guideline for experiments

Lang，Zhongling1; Miao，Jun2; Tan，Huaqiao1; Su，Zhongmin1,3; Li，Yangguang1; Zheng，Zhiping2

2020-11-21

10.1039/d0qi01014f

Inorganic Chemistry Frontiers   影响因子和分区

2052-1553

2052-1553

The electrochemical NO reduction (NOER) is one of the most promising routes for ammonia synthesis and for simultaneously removing the air pollutant, NO. However, the current electro-catalysts are mainly metal based, and the search for new and cost-efficient NOER catalysts is in the pipeline. Polyoxometalates, a class of metal-oxide clusters, exhibiting unique electrochemical redox behavior, have been widely applied to many electrocatalytic processes. In this work, density functional theory (DFT) calculations were adopted to investigate the NOER performance of a series of transition metal-substituted (TMPOMs, FeII ∼ CuII, RuII ∼ AgI, OsII ∼ AuI) heteropolytungstates. Firstly, we take the highly active SiW11FeII catalyst reported in experiments as an example to investigate its detailed NOER mechanism, and thus provide some qualitative criteria for screening potential new NOER catalysts. The ∗NHO and ∗NHOH intermediates are confirmed based on their lower energies compared to ∗NOH and ∗NH2O, respectively. The high activity and ammonia selectivity of SiW11FeII are dominated by four factors: (i) a moderate NO adsorption ability, (ii) an acceptable N-O bond activation barrier (ΔGb = 0.65 eV) at room temperature, (iii) low onset potential for the potential-limiting step (ca. -0.21 V), and (iv) effective suppression of the competitive HER and N2O formation reaction. Inspired by this, NiII-, CoII-, CuII-, PdII-, PtII-, and AgI-substituted heteropolytungstates are identified as candidate electrocatalysts for application in the NOER through a comprehensive comparison with the SiW11FeII case. Particularly, SiW11NiII was selected as the most optimal with an extremely low ΔGb of only 0.07 eV for the ∗NO → ∗NHO step. It is suggested that the high electrocatalytic activity of SiW11NiII originates from its high reduction ability to accept electrons in the electrocatalytic process, and the low basicity strength of O sites to promote the transfer of H. The present work provides an expansion of the POMs' family in the field of NOER, and ultimately facilitates the designing of nitrogen-cycle catalysts for targeted environmental and synthesis applications. This journal is

SCI ; EI

英语

其他

National Natural Science Foundation of China[21771033][21671036][21901035] ; Fundamental Research Funds for the Central Universities[2412018BJ001][2412018ZD007][2412018QD005] ; China Postdoctoral Science Foundation[2018M631849] ; Foundation of Jilin Educational Committee[JJKH20190268KJ] ; Scientific Development Project of Jilin Province[20190201206JC] ; Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; SUSTech[Y01216127][Y01216227]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000587892200019

ROYAL SOC CHEMISTRY

20204709503143

Nitric oxide ; Alkalinity ; Density functional theory ; Reduction ; Pollution control ; Silicon compounds ; Ammonia ; Chemical bonds ; Transition metals

Metallurgy and Metallography:531 ; Chemistry, General:801.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

2-s2.0-85096114304

Scopus

1.Key Laboratory of Polyoxometalate Science of the Ministry of Education,Faculty of Chemistry,Northeast Normal University,Changchun,130024,China
2.Guangdong Provincial Key Laboratory of Catalysis,Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen Guangdong,518000,China
3.Jilin Provincial Science and Technology Innovation Center of Optical Materials and Chemistry,School of Chemistry and Environmental Engineering,Changchun University of Science and Technology,Changchun,130022,China

Lang，Zhongling,Miao，Jun,Tan，Huaqiao,et al. Element table of TM-substituted polyoxotungstates for direct electrocatalytic reduction of nitric oxide to ammonia: A DFT guideline for experiments[J]. Inorganic Chemistry Frontiers,2020,7(22):4507-4516.

Lang，Zhongling,Miao，Jun,Tan，Huaqiao,Su，Zhongmin,Li，Yangguang,&Zheng，Zhiping.(2020).Element table of TM-substituted polyoxotungstates for direct electrocatalytic reduction of nitric oxide to ammonia: A DFT guideline for experiments.Inorganic Chemistry Frontiers,7(22),4507-4516.

Lang，Zhongling,et al."Element table of TM-substituted polyoxotungstates for direct electrocatalytic reduction of nitric oxide to ammonia: A DFT guideline for experiments".Inorganic Chemistry Frontiers 7.22(2020):4507-4516.