Clever Nanomaterials Fabrication Techniques Encounter Sustainable C1 Catalysis

Abstract

Conspectus C1 catalysis, which refers to the conversion of molecules with a single carbon atom, such as CO, CO2, and CH4, into clean fuels and basic building blocks for chemical industries, has built a bridge between carbon resource utilization and valuable chemical supply. With respect to the goal of carbon neutrality, C1 catalysis also plays an essential role owing to its integrated functions in the green catalytic process with fewer CO2 emissions and even direct high-value-added utilization of greenhouse gases (CO2 and CH4). However, the inert nature of the C–O or C–H bond in C1 molecules as well as uncontrollable C–C coupling render C1 catalysis challenging. The rational design of highly active catalytic materials (denoted as C1 catalysts) with strong capacities for C–O or C–H bond activation and C–C coupling by convenient nanomaterials fabrication methods to boost the catalytic performance of C1 molecule conversion, including targeted product selectivity and long-term stability, is the cornerstone of C1 catalysis. Notably, the familiar concepts in heterogeneous catalysis, such as tandem catalysis and confinement catalysis, are applicable for C1 catalysis and have been successfully used to design a C1 catalyst. Regarding the tandem catalysis concept that integrates multiple reactions in a single-pass via a bi- or multifunctional catalyst, it is promising to shed new light on the oriented conversion of C1 molecules, especially for C2+ hydrocarbon or oxygenate synthesis. The confinement effect is powerful for controlling the product distribution and enhancing activation efficiency of inert chemical bonds in C1 catalysis due to the unique reactants/intermediate adsorption and evolution behaviors on the confined catalytic interface with a special electronic environment. Moreover, metal–support interactions (MSIs), electronic properties of the active site, and catalytic engineering issues are also susceptible to the C1 molecule conversion performance. Therefore, under the guidance of basic and novel rules in heterogeneous catalysis, the innovation of catalytic materials with the aid of advanced catalytic materials fabrication techniques has always been a hot research topic in C1 catalysis. In this Account, we briefly describe the challenges in thermal–catalytic C1 molecule (mainly CO, CO2, and CH4) conversion. At the same time, the synergistic functioning of the physicochemical properties of the catalytic materials on the performance in C1 molecule conversion is highlighted. More importantly, we summarize our progress in rationally designing tailor-made C1 catalysts to enhance C1 molecule activation efficiency and targeted product selectivity via powerful nanomaterials fabrication techniques, such as traditional wet-chemistry strategies, the magnetron sputtering method, and 3D printing technology. Specifically, the ingenious capsule catalyst and ammonia pools in zeolites fabricated by a wet chemistry process possess an extraordinary effect on the transformation of CO, CO2, and CH4 molecules. Also, the sputtering m...

Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion

“… 1 , 2 The current main conversion pathways for C1 molecules into valuable chemicals and fuels are shown in Figure 1 . 3 Syngas (CO + H 2 ) from the gasification of coal, biomass, and natural gas can be converted into platform chemicals (e.g., methanol, alkanes, and alkenes) via the direct pathway, as well as value-added products (e.g., aromatics, transportation fuels, light olefins, etc.) via the indirect process.…”

“…

Figure 1 The conversion pathways for different C1 molecules to valuable chemicals Reproduced with permission from Wang et al. 3 Copyright © 2023, American Chemical Society.

…”

Introduction of TiO2 enhancing the catalytic performance of Ti(SO4)2/SiO2 for dimethyl ether oxidation

“…into a variety of high-value-added fuels and chemicals has been paid extensive attention. 1 Dimethyl ether (DME) is an excellent clean fuel and also an important platform compound. 2 Therein, dimethoxymethane (DMM), as one of the downstream products of DME, is a green organic solvent with low toxicity and excellent dissolving properties, which can be widely used in energy and chemical fields.…”