摘要
Thermally assisted photodriven nitrogen oxidation to nitric oxide(NO)using air as a reactant is a promising way to supersede the traditional NO synthesis industry accompanied by huge energy expenditure and greenhouse gas emission.Meanwhile,breaking the N≡N triple bond(941 kJ·mol^(−1))in nitrogen is still challenging,and the development of more efficient catalysts is necessary.Herein,Ru single atoms decorated TiO_(2) nanosheets(Ru SAs/TiO_(2))were constructed and achieved superior performance for NO photosynthesis with a product rate of 192μmol g^(−1) h^(−1) and a quantum efficiency of 0.77% at 365 nm.Both ^(15)N isotope labeling experiments and in situ near ambient pressure X-ray photoelectron spectroscopy(in situ NAP-XPS)proved the origin of NO from N_(2) photooxidation.A series of in situ characterizations and theoretical calculations unveiled the reaction pathway of nitrogen photooxidation.Breaking the O-O bond to form(N-O)2-Ru intermediates was demonstrated as the rate-determining step.Importantly,a single-atomic structure was proven to inhibit the aggregation and inactivation of Ru,leading to outstanding durability.
基金
financially supported by the National Natural Science Foundation of China(nos.22071173 and 21871206)
the Natural Science Foundation of Tianjin City(no.17JCQNJC03200).
