Electronic Regulation of Bromophenyl Grafted Metal‐Free Carbon Nitride Catalysts for Enhanced Utilization of H₂S

Abstract

Developing metal‐free heterogeneous catalysts with high efficiency for the elimination of H2S into eco‐friendly products are very important for both fundamental catalytic science and industrial chemistry. Herein, we design a new modified carbon nitride catalyst engrafted with Br‐substituted aromatic heterocycle (CNU−Br) through a simple copolymerization and exfoliation method. CNU−Br exhibits excellent H2S conversion efficiency, high sulfur selectivity, and outstanding stability in the catalytic desulfurization reaction, which is better than most of the reported catalysts. The experiments and theoretical calculations show that the grafting of bromophenyl groups into the fundamental carbon nitride structural network leads to π‐delocalization, surface modification, as well as enhances the basicity of the structural active N sites. The regulation of the H and S affinity of CNU−Br that mediate the facile cleavage of H2S hydrogen‐sulfur bonds and the release of S atoms in thermodynamics. Furthermore, the superior surface area and mass transfer over CNU−Br accelerate the adsorption and oxidation of H2S in kinetics compared with the ordinary carbon nitride.

Counterion chemistry of 5-halo (X: Cl, Br, I)-uracil derived carbon nitride: unlocking enhanced photocatalytic performance

“…The highresolution Br 3d spectra of the BUCN catalyst is deconvoluted into three peaks located at 70.9, 68.4, and 66.9 eV. The two peaks at 70.9 and 68.4 eV can be assigned to the C-Br 3d 3/2 and C-Br 3d 5/2 covalent bonds, respectively, 43,44 while the third peak at 66.9 eV is likely from the ionic C-Br + 3d 5/2 bond. 45 The existence of ionic or semi-ionic bonds contributes signicantly to improving the catalytic activity.…”

Highly Poison‐Resistant Single‐Atom Co–N4 Active Sites with Superior Operational Stability over 460 h for H2S Catalytic Oxidation

“…The massive consumption of fossil energy has increased the emission of toxic H 2 S, inevitably leading to serious environmental problems. [1][2][3] The selective catalytic oxidation of H 2 S with O 2 represents a facile and efficient strategy for the elimination of H 2 S. [4] Meanwhile, when coordination bonds formed between Co and N, the interactions between the geometric and electronic would lead to a more optimized structures, which makes it possible for the adsorption and desorption of the reaction intermediate to reach an appropriate state. [30,31] In this regard, it would be quite attractive to investigate the single-atom Co-N X catalyst for H 2 S selective oxidation.…”

Enabling High Efficiency and Rapid Regeneration of α-FeOOH@Fe-EDTA for Slurry Desulfurization

“…Traditional chemical processes such as blast furnace gas, natural gas, and fuel gas contain various sulfur impurities including hydrogen sulfide (H 2 S), carbonyl sulfides (COS), methyl mercaptan (CH 4 S), and dimethyl sulfide (C 2 H 6 S). − They are highly nocuous and strongly corrosive, inevitably affecting industrial operational safety and causing environmental pollution problems. , Among these sulfides, H 2 S has become the main removal target due to its high concentration and large total amount . In this regard, the high-efficiency elimination of H 2 S becomes a key step for the clean and efficient use of fossil energy.…”