First-principles study of CO2 hydrogenation to formic acid on single-atom catalysts supported on SiO2.

The hydrogenation of CO2 into valuable chemical fuels reduces the atmospheric CO2 content and also has broad economic prospects. Support is essential for catalysts, but many of the reported support materials cannot meet the requirements of accessibility and durability. Herein, we theoretically designed a series of single-atom noble metals anchored on a SiO2 surface for CO2 hydrogenation using density functional theory (DFT) calculations. Through theoretical evaluation of the formation energy, hydrogen dissociation capacity, and activity of CO2 hydrogenation, we found that Ru@SiO2 is a promising candidate for CO2 hydrogenation to formic acid. The energy barrier of the rate-determining step of the entire conversion process is 23.9 kcal mol-1; thus, the reaction can occur under mild conditions. In addition, active and stable origins were revealed through electronic structure analysis. The charge of the metal atom is a good descriptor of the catalytic activity. The Pearson correlation coefficient (PCC) between metal charge and its CO2 hydrogenation barrier is 0.99. Two solvent models were also used to investigate hydrogen spillover processes and the reaction path was searched by the climbing image nudged-elastic-band (CI-NEB) method. The results indicated that the explicit solvent model could not be simplified into a few solvent molecules, leading to a large difference in the reaction paths. This work will serve as a reference for the future design of more efficient catalysts for CO2 hydrogenation.

An Effective Strategy to Boost Formic Acid Dehydrogenation over Pd/AC-NH2 Catalyst through Pd Size Control.

Formic acid (FA, HCOOH) is regarded as one of the most promising carriers for hydrogen storage. However, the catalyst design for FA dehydrogenation into H2 with high efficiency is not clear. Here, we elucidate the rationale of size effect over the most commonly used Pd-based catalyst through supporting different Pd species, including single atoms, nanoclusters, and nanoparticles, on amine-functionalized active carbon (Pd/AC-NH2). The activity test presents that Pd/AC-NH2 with Pd nanoclusters exhibits the best turnover frequency (TOF) value of 40856 h-1 for 1 M FA at 328 K and even 1504 h-1 for neat FA at 308 K, which is comparable to the homogeneous catalysts and has been the first heterogeneous catalyst used in neat FA dehydrogenation under mild conditions. The comprehensive characterizations reveal that the size of Pd species affects the ratios of Pd0/Pd2+ and hydrogen spillover effect, which is crucial for the C-H cleavage and H2 desorption. Besides, the influences of amine groups on catalytic performance were further examined. This work provided an ingenious guideline to design efficient and practical catalysts for hydrogen storage under ambient conditions.

Highly Stable Cesium Molybdenum Chloride Perovskite Nanocrystals for Photothermal Semihydrogenation Applications.

Metal halide perovskite materials with excellent carrier transport properties have been regarded as a new class of catalysts with great application potential. However, their development is hampered by their instability in polar solvents and high temperatures. Herein, we report a solution-processed Cs2MoCl6 perovskite nanocrystals (NCs) capped with the Mo6+, showing high thermostability in polar solvents. Furthermore, the Pd single atoms (PdSA) can be anchored on the surface of Cs2MoCl6 NCs through the unique coordination structure of Pd-Cl sites, which exhibit excellent semihydrogenation of different alkyne derivatives with high selectivity at full conversion at room temperature. Moreover, the activity could be improved greatly under Xe lamp irradiation. Detailed experimental characterization and DFT calculations indicate the improved activity under light illumination is due to the synergistic effect of photo-to-heat conversion and photoinduced electron transfer from Cs2MoCl6 to PdSA, which facilitates the activation of the C≡C group. This work not only provides a new catalyst for high selective semihydrogenation of alkyne derivatives but also opens a new avenue for metal halides as photothermal catalysts.

Protocol for ambient CO2 capture and conversion into HCOOH and NH4H2PO4.

CO2 capture and utilization into liquid fuels and high-added-value chemicals has been regarded as an attractive strategy to mitigate excessive carbon emissions. Here, we present a protocol to capture and convert CO2 into pure formic acid (HCOOH) solution and solid fertilizer (NH4H2PO4). We describe steps for synthesis of an IRMOF3-derived carbon-supported PdAu heterogeneous catalyst (PdAu/CN-NH2), which can efficiently catalyze (NH4)2CO3-captured CO2 into formate under ambient conditions. For complete details on the use and execution of this protocol, please refer to Jiang et al. (2023).1.

Liquid Sunshine: Formic Acid.

"Liquid sunshine" is the conceptual green liquid fuel that is produced by a combination of solar energy, CO2, and H2O. Alcohols are commonly regarded as the preferred candidates for liquid sunshine because of their advantages of high energy density and extensive industrial applications. However, both the alcohol synthesis and H2 release processes require harsh reaction conditions, resulting in large external energy input. Unlike alcohols, the synthesis and dehydrogenation of formic acid (FA)/formate can be performed under mild conditions. Herein, we propose liquid sunshine FA/formate as a promising supplement to alcohol. First, we outline the vision of using FA/formate as liquid sunshine and discuss its feasibility. Then, we concentrate on the application of FA/formate as liquid organic hydrogen carrier and summarize the recent developments of CO2 hydrogenation to FA/formate and FA/formate dehydrogenation under mild conditions. Finally, we discuss the current applications, challenges, and opportunities surrounding the use of FA/formate as liquid sunshine.

Rational Design of Synergistic Structure Between Single-Atoms and Nanoparticles for CO2 Hydrogenation to Formate Under Ambient Conditions.

Single-atom catalysts (SACs) as the new frontier in heterogeneous catalysis have attracted increasing attention. However, the rational design of SACs with high catalytic activities for specified reactions still remains challenging. Herein, we report the rational design of a Pd1-PdNPs synergistic structure on 2,6-pyridinedicarbonitrile-derived covalent triazine framework (CTF) as an efficient active site for CO2 hydrogenation to formate under ambient conditions. Compared with the catalysts mainly comprising Pd1 and PdNPs, this hybrid catalyst presented significantly improved catalytic activity. By regulating the ratio of Pd1 to PdNPs, we obtained the optimal catalytic activity with a formate formation rate of 3.66 molHCOOM·molPd -1·h-1 under ambient conditions (30°C, 0.1 MPa). Moreover, as a heterogeneous catalyst, this hybrid catalyst is easily recovered and exhibits about a 20% decrease in the catalytic activity after five cycles. These findings are significant in elucidating new rational design principles for CO2 hydrogenation catalysts with superior activity and may open up the possibilities of converting CO2 under ambient conditions.