Catalysis by Supported Gold Nanoparticles: Beyond Aerobic Oxidative Processes

Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because of the extreme inertness of CO2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst.

Oil and water: A new energy-efficient and atom-economical catalytic route for the production of alkanes and methanol by upgrading the phenolic fraction of bio-oil has been developed. The one-pot aqueous-phase hydrodeoxygenation process is based on two catalysts facilitating consecutive hydrogenation, hydrolysis, and dehydration reactions.

Highly Selective Catalytic Conversion of Phenolic Bio‐Oil to Alkanes

Considerable worldwide interest exists in discovering renewable energy sources that can substitute for fossil fuels. Lignocellulosic biomass, the most abundant and inexpensive renewable feedstock on the planet, has a great potential for sustainable production of fuels, chemicals, and carbon-based materials. Fast pyrolysis integrated with hydrotreating, one of the simplest, most cost-effective, and most efficient processes to convert lignocellulosic biomass to liquid hydrocarbon fuels for transportation, has attracted significant attention in recent decades. However, effective hydrotreating of pyrolysis bio-oil presents a daunting challenge to the commercialization of biomass conversion via pyrolysis-hydrotreating. Specifically, the development of active, selective, and stable hydrotreating catalysts is problematic due to the poor quality of current pyrolysis bio-oil feedstock (i.e., high oxygen content, molecular complexity, coking propensity, and corrosiveness). Significant research has been conducted to...

Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds

Isolated atoms featuring unique reactivity are at the heart of enzymatic and homogeneous catalysts. In contrast, although the concept has long existed, single-atom heterogeneous catalysts (SACs) have only recently gained prominence. Host materials have similar functions to ligands in homogeneous catalysts, determining the stability, local environment, and electronic properties of isolated atoms and thus providing a platform for tailoring heterogeneous catalysts for targeted applications. Within just a decade, we have witnessed many examples of SACs both disrupting diverse fields of heterogeneous catalysis with their distinctive reactivity and substantially enriching our understanding of molecular processes on surfaces. To date, the term SAC mostly refers to late transition metal-based systems, but numerous examples exist in which isolated atoms of other elements play key catalytic roles. This review provides a compositional encyclopedia of SACs, celebrating the 10th anniversary of the introduction of this term. By defining single-atom catalysis in the broadest sense, we explore the full elemental diversity, joining different areas across the whole periodic table, and discussing historical milestones and recent developments. In particular, we examine the coordination structures and associated properties accessed through distinct single-atom-host combinations and relate them to their main applications in thermo-, electro-, and photocatalysis, revealing trends in element-specific evolution, host design, and uses. Finally, we highlight frontiers in the field, including multimetallic SACs, atom proximity control, and possible applications for multistep and cascade reactions, identifying challenges, and propose directions for future development in this flourishing field.

Single-Atom Catalysts across the Periodic Table.

We show that long-chain 1-alcohols can be produced with high selectivities using heterogeneous CO hydrogenation catalysis. This breakthrough is achieved through the targeted design of “CoCuMn” nanosized core–shell particles using co-precipitation of metal salts into oxalate precursors and subsequent thermal decomposition. Using stoichiometric CO/H2 feeds, the selectivities to 1-alcohols or combined 1-alcohols/1-alkenes are usually higher than 60% and occasionally up to 95%. The Anderson–Schulz–Flory chain-lengthening probabilities for these products are higher than 0.6, but usually below 0.9 so as to optimize the C8–C14 slate as feedstock for plasticizers, lubricants, or detergents.

Long-chain terminal alcohols through catalytic CO hydrogenation.

The catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ∼97% can be n-aldehydes. While the product slate contains ∼60% n-aldehydes at /pCO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson–Schulz–Flory behaviour, independent of the /pCO ratio, is found for the sum of C4+ products. We advocate a synergistic interaction between a Mn5O8 oxide and a bulk Co2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies. The catalytic CO hydrogenation traditionally produces mainly methanol and long-chain hydrocarbons. Here, the authors show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts.

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Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

Bimetallic CoCu model catalysts were investigated for the synthesis of higher alcohols using catalytic CO hydrogenation according to the Fischer–Tropsch technology. Emphasis was placed on revealing the influence of the activation conditions. Accordingly, catalyst precursors were activated in argon, hydrogen, syngas (CO/H2), and CO under atmospheric conditions and at elevated temperatures (370 °C). All catalyst precursors were prepared via oxalate coprecipitation in the absence of a classic support. Alcohol selectivities between 30 and ∼40% (up to ∼50% for the sum of alcohols and alkenes) were obtained with an Anderson–Schulz–Flory (ASF) chain lengthening probability maximizing the slate up to C6. Detailed catalysis and characterization studies were performed using a Co2Cu1 catalyst composition. The catalytic performances of the H2- and syngas-activated Co2Cu1 catalyst were similar. While the CO-activated catalyst shows significantly higher catalytic activity and ASF chain lengthening probability, the alco...

Yizhi Xiang

Papers

Long-chain terminal alcohols through catalytic CO hydrogenation.

Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

Higher Alcohols through CO Hydrogenation over CoCu Catalysts: Influence of Precursor Activation

Progress and prospects in catalytic ethane aromatization

Aqueous system for the improved hydrogenation of phenol and its derivatives