Direct CO₂ hydrogenation offers an important strategy for promoting the global carbon balance, but high thermodynamic and kinetic stability of CO₂ has restricted its applicability to only a handful of industrial sectors. Here, we introduce a proof-of-concept application of the electron-rich Pt surface to promote hydrogen donation for electron-rich MoC particles acting as hydrogen acceptors, thereby constructing hydrogen-rich surface of MoC active centers. Moreover, the formed hydrogen-rich and electron-rich surface could greatly decrease reaction activation energy to boost the efficient CO₂ hydrogenation into formic acid over the MoC centers. The optimized MoC@NC/Pt-0.1 catalyst exhibits a high turnover frequency (TOF) value of 1.2 h^–1 at a lower temperature of 60 °C, and TOF of 24.2 h^–1 under standard reaction conditions widely used in the literature, exceeding 7 times for MoC@NC catalyst, and surpassing the benchmark classical non-noble metal active center-based heterogeneous catalyst.

Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in catalytic hydrogenation systems to produce polymers, pharmaceuticals, agrochemicals, fragrances, and biofuels at million-ton scale. Much attention has been paid to the design of the more active catalytic site to effectively adsorb and activate reactants and H₂ molecules. At the same time, there is still a huge room to develop powerful strategies to accelerate the donation of acted H species to the reactants from the Pt surface further to boost the final catalytic efficiencies of Pt catalysts and depress the total Pt consumption. Herein, we present a new strategy for promoting the Pt–H bond dissociation by increasing surface hydrogen coverage on designed electron-deficient Pt nanoparticles. The electron deficiency of Pt nanoparticles has been successfully tuned by constructing a rectifying contact with an even “noble” boron-rich carbon support (Pt/BC). Theoretical and experimental results confirm the dominant role of the pronounced electron deficiencies of Pt nanoparticles in enhancing the H coverage for 2.3 times higher than that of neutral Pt nanoparticles, significantly boosting the Pt–H bond dissociation and thus the whole hydrogenation process as reflected by the extremely high turnover frequency (TOF) value of 388 h⁻¹ at 30 °C and 10 bar H₂ for phenol hydrogenation on the Pt/BC, outperforming the bench-marked catalysts by a factor of 9.

Visible and even infrared (IR) light-initiated hot electrons of graphene (Gr) catalysts are a promising driven power for green, safe, and sustainable H₂O₂ synthesis and organic synthesis without the limitation of bandgap-dominated narrow light absorption to visible light confronted by conventional photocatalyst. However, the life time of photogenerated hot electrons is too short to be efficiently used for various photocatalytic reactions. Here, we proposed a straightforward method to prolong the lifetime of photogenerated hot electrons from graphene by tuning the Schottky barrier at Gr/rutile interface to facilitate the hot electron injection. The rational design of Gr-coated TiO₂ heterojunctions with interface synergy-induced decrease in the formation energy of the rutile phase makes the phase transfer of TiO₂ support proceed smoothly and rapidly via ball milling. The optimized Gr/rutile dyad could provide a H₂O₂ yield of 1.05 mM·g⁻¹·h⁻¹ under visible light irradiation (λ ≥ 400 nm), which is 30 times of the state-of-the-art noble-metal-free titanium oxide-based photocatalyst, and even achieves a H₂O₂ yield of 0.39 mM·g⁻¹·h⁻¹ on photoexcitation by near-infrared-region light (~ 800 nm).

The rational design of highly active and stable atomically dispersed M-X₄ (M = Fe, Co, Ni, etc., X = C, N) -based catalysts holds promises for wide application in almost all realms of catalysis. Despite great effort in the construction of specific M-X₄ centers, the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored. Herein, we develop a new type of M-X₄ catalyst composed of Fe-N₄ centers and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N₄ centers in tailoring their electron density and final catalytic selectivity. The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N₄ centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines. As a reusable heterocatalyst, the state-of-the-art FeNC+B catalyst provides a turn-over frequency (TOF) value of 21.6 mol_benzonitrile·mol_Fe^-1·h^-1 (100 °C), outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.

The greenhouse effect and global warming are serious problems because the increasing global demand for fossil fuels has led to a rapid rise in greenhouse gas exhaust emissions in the atmosphere and disruptive changes in climate. As a major contributor, CO₂ has attracted much attention from scientists, who have attempted to convert it into useful products by electrochemical or photoelectrochemical reduction methods. Facile design of efficient but inexpensive and abundant catalysts to convert CO₂ into fuels or valuable chemical products is essential for materials chemistry and catalysis in addressing global climate change as well as the energy crisis. Herein, we show that two-dimensional fewlayer graphitic carbon nitride (g-C₃N₄) can function as an efficient metal-free electrocatalyst for selective reduction of CO₂ to CO at low overpotentials with a high Faradaic efficiency of ~ 80%. The polarized surface of ultrathin g-C₃N₄ layers (thickness: ~ 1 nm), with a more reductive conduction band, yields excellent electrochemical activity for CO₂ reduction.

In this work, we described a proof-of-concept method to promote the activity and selectivity of Pd nanoparticles for heterogeneous catalysis (exemplified by C–C coupling reactions) by using acid sites within a zeolite framework. The Pd nanoparticles were encapsulated inside the crystalline walls of mesoporous H-ZSM-5 leading to hybrid samples (denoted as Pd@mZ-x-H) with controlled number of acid sites. A linear relationship between the number of acid sites of the zeolite nanocrystals and the catalytic activities of the Pd nanoparticles in organic reactions was established. Moreover, the shape-dependent selectivity of Pd@mZ-x-H was not sacrificed when the final activity was enhanced.

A facile method was developed to fabricate nitrogen-doped graphene microtubes (N-GMT) with ultra-thin walls of 1–4 nm and large inner voids of 1–2 μm. The successful introduction of nitrogen dopants afforded N-GMT more active sites for significantly enhanced hydrogen evolution reaction (HER) activity, achieving a current density of 10 mA·cm^–2 at overpotentials of 0.464 and 0.426 V vs. RHE in 0.1 and 6 M KOH solution, respectively. This HER performance surpassed that of the best metal-free catalyst reported in basic solution, further illustrating the great potential of N-GMT as an efficient HER catalyst for real applications in water splitting and chlor-alkali processes.