In this study, a novel non-metallic carbon-based catalyst co-doped with boron and nitrogen (B,N) was successfully synthesized. By precisely controlling the carbonization temperature of a binary mixed ionic liquid, we selectively modified the doping site structure, ultimately constructing a B,N co-doped frustrated Lewis acid-base pair catalyst. This catalyst exhibited remarkable catalytic activity, selectivity, and stability in the dehydrochlorination reaction of 1,1,2-trichloroethane (TCE). Detailed characterization and theoretical calculations revealed that the primary active center of this catalyst was the BN₃ configuration. Compared to conventional graphitic N structures, the BN₃ structure had a higher p-band center, ensuring superior adsorption and activation capabilities for TCE during the reaction. Within the BN₃ site, three negatively charged nitrogen atoms acted as Lewis bases, while positively charged boron atoms acted as Lewis acids. This synergistic interaction facilitated the specific dissociation of chlorine and hydrogen atoms from TCE, significantly enhancing the 1,1-dichloroethene selectivity. Through this research, we not only explored the active site structure and catalytic mechanism of B,N co-doped catalysts in depth but also provided an efficient, selective, and stable catalyst for the dehydrochlorination of TCE, contributing significantly to the development of non-metallic catalysts.

Synergistic catalysis opens up a new venue to improve the comprehensive application of the catalyst. Herein, a composite catalyst (Mo-Pd@N-C) consisting of the N-doped carbon derived from pyrolysis of spherical polypyrrole and MoPd nanoparticles (NPs) was constructed to emphasize the strong metal–support interaction for robust oxygen reduction reaction (ORR). The enhanced anchoring between the MoPd NPs and the substrate, and the N-species formed on the carbon matrix make the Mo-Pd@N-C deliver excellent performance with a half-wave potential of 0.945 V (vs. reversible hydrogen electrode (RHE)) for ORR, superior than that of commercial Pt/C (0.86 V). More importantly, it shows a negligible half-wave potential decline (< 5 mV) and only ~ 20% of mass activity (MA) attenuation after 30,000 cycles stability test, obviously better than those of Pt/C (~ 70% of MA attenuation and ~ 30 mV of half-wave potential decline after only 15,000 cycles). This work highlights a novel synergistic method to prolong the life and improve the commercial prospects of the catalysts.

Oxidative couplings of aliphatic alkynes are crucial for the production of naturally occurring 1,3-diynes. Herein we report the novel approach for effective synthesis of unsaturated coordinated N doped copper oxides (N-CuO_x) catalyst, and uncover that N-CuO_x catalyst as an additive-free and cost-effective heterogeneous catalyst has highly catalytic performance for directly oxidative coupling of aliphatic alkynes. The key to achieve efficient oxidative coupling of aliphatic alkynes is the synergistic effect of N species and uncoordinated O/Cu species caused by N dopants, which undergoes the Langmuir–Hinshelwood reaction mechanism. The N-CuO_x catalyst displays ~ 89.1% yield for hexadeca-7,9-diyne under mild conditions and stable reusability (5 cycles), showing significant advances compared with the traditionally copper oxides. These findings highlight the heteroatom dopants that provide a new methodology for designing efficient copper catalysts in synthesis of naturally occurring 1,3-diynes.

Electrochemical upgrading of biomass ethanol to value-added chemicals is promising for sustainable society. Here, we synthesize defective Ni₃S₂ nanowires (NWs), which show high activity towards electrochemical oxidation of ethanol to acetate. The Ni₃S₂ NWs are formed by the oriented attachment mechanism, and rich defects are introduced during the growth. A low onset potential of 1.31 V and high mass activity of 8,716 mA·mg_Ni⁻¹ at 1.5 V are achieved using the synthesized Ni₃S₂ NWs toward the ethanol electro-oxidation, which are better than the Ni(OH)₂ NWs and the Ni₃S₂ nanoparticles (NPs). And the selectivity for the acetate generation is ca. 99%. The high activity of Ni₃S₂ NWs is attributed to the easier oxidation of Ni(II) to the catalytically active Ni(III) species with the promotion from S component and rich defects. These results demonstrate that the defective NWs can be synthesized by the oriented attachment method and the defective Ni₃S₂ NWs structure as the efficient non-noble metal electrocatalysts for oxidative upgrading of ethanol.

Rational design of earth-abundant transition metal oxides catalysts is highly desirable for developing sustainable chemical processes. Herein, we demonstrate a prospective interstitial nitrogen engineering for fabricating oxygen vacancies (OVs)-rich nitrogen-doped-Mn_xCo_3-xO₄ (N-Mn_xCo_3-xO₄) oxide catalyst, in which the ratio of OVs concentration of N-Mn_xCo_3-xO₄ to Mn species is as high as 1:1, according to the characterizations of X-ray absorption (XAS) and X-ray photoelectron (XPS) spectroscopies. The promising strategy of interstitial nitrogen engineering through lattice distortion caused by the Jahn-Teller effect can significantly increase the amount of interstitial nitrogen. The resulting catalyst enables an additive-free aerobic dehydrogenation coupling of aromatic amine to afford azo compounds with > 99% yield and > 99% selectivity at 60 °C. We observed the superb catalytic activity is promoted by the enhanced oxygen mobility in OVs, which were created by the interstitial nitrogen in the catalyst matrix. The presence of interstitial nitrogen in transition metal oxides in this study shows how the manipulation of catalyst matrix can increase the OV sites to promote aerobic oxidation reaction.

Heterostructured bimetal nanocrystals with a component having localized surface plasmon resonance (LSPR) property are promising photocatalysts for a series of reactions. In this work, kinetic products of Pd-Ag with a screwdriver-like heterostructure have been successfully fabricated via the selective epitaxial growth of Ag on Pd nanowires (NWs). It was confirmed that the deposition rate (V_deposition) of Ag is much more sensitive to the temperature, compared to the surface diffusion rate (V_diffusion) which can be effectively reduced by the binding of poly(vinylpyrrolidone) (PVP) molecules. Then the magnitude of V_deposition/V_diffusion has been well tailored for the formation of a kinetic growth environment. The interactions between the components of the as-prepared Pd-Ag heterostructures resulted in intensified LSPR effects. As a result, they gained better photocatalytic performance toward solvent free aerobic oxidation of toluene than Pd NWs, Ag NWs and the mixture of them. Additionally, the Pd-Ag heterostructured nanocrystals exhibited excellent catalytic stability for recycling. This work not only presents an idea for realizing kinetic growth but also supports that LSPR effect is a good tool for improving the photocatalytic activity.

Developing non-precious metal catalysts with high activity and stability for electrochemical hydrogen evolution reaction (HER) is of great significance in both science and technology. In this work, N-doped CMK-3, which was prepared with a casting method using SBA-15 as the hard template and ammonia as the nitrogen source, has been utilized to hold MoS₂ and restrict its growth to form MoS₂@N-CMK-3 composite. As a result, MoS₂ was found to have poorly crystallized and the limited space of porous N-CMK-3 made its size much small. Then there are more active sites in MoS₂. Accordingly, MoS₂@N-CMK-3 has exhibited good electrocatalytic performance toward HER in acids with a quite small Tafel slope of 32 mV·dec^-1. And more importantly, compared to MoS₂@CMK-3, its stability has been greatly improved, which can be attributed to the interaction between MoS₂ and nitrogen atoms avoiding aggregation and mass loss. This work provides an idea that doping a porous carbon support with nitrogen is an effective way to enhance the stability of the catalyst.

Controlling the size of SBA-15 can be beneficial for exploiting CMK-3, which has excellent structural parameters, for better performance in adsorption and/or catalytic processes. In this study, the width of freestanding SBA-15 rods was readily and successfully regulated by simply altering the stirring power during the synthesis. A higher stirring rate produced SBA-15 rods with larger width. Then, the size of the CMK-3 rods was adjusted by duplication of the different-sized SBA-15. The results show that the larger sized CMK-3 has higher specific surface area and pore volume, which led to a higher adsorption capacity and a faster adsorption rate. It is believed that the synthetic method reported here is powerful for developing better mesoporous carbon for application in water purification and catalysis.

Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon (Pd@CMK-3) has been prepared by a strategy involving immersion, ammoniahydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd(0) and Pd(Ⅱ) species co-exist and were embedded in the matrix of the porous carbon (CMK-3). The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency (TOF) could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.