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In the chemical industry, formaldehyde is an important bulk chemical. The traditional synthesis of formaldehyde involves an energy intensive oxidation of methanol over a metal oxide catalyst. The selective electrochemical oxidation of methanol is challenging. Herein, we report a catalytic system with an immobilized TEMPO electrode that selectively oxidizes methanol to formaldehyde with high turnover numbers. Upon the addition of various organic and inorganic bases, the activity of the catalyst could be tuned. The highest Faradaic efficiency that was achieved was 97.5 %, the highest turnover number was 17100. Additionally, we found that the rate determining step changed from the step in which the carbonyl specie is created from the methanol‐TEMPO adduct to the oxidative regeneration of the TEMPO+ species. Finally, we showed that the system could be applied to the oxidation of other aliphatic alcohols. [ABSTRACT FROM AUTHOR]

The challenge of moving to a carbon-free energy economy is highlighted in the context of technology and materials restrictions. Many technologies needed for the so-called energy transition depend on critical metals such as platinum, lithium, iridium and cobalt. Here we focus on solid borohydride salts as hydrogen carriers, studying catalysts for hydrogen release. We combine metal 3D printing technology and a Raney-type leaching process to make structured macroscopic catalyst/reactor monoliths of cobalt, aluminium and stainless steel with well-defined micropores. Remarkably, the blank catalyst samples, which are made only from aluminium and stainless steel (Al-SS), show high activity and, importantly, high stability in borohydride hydrolysis, with no mass loss and no surface poisoning. The batch results are confirmed in a continuous setup running for 96 h. Catalyst performance is attributed to the stable porous structure, the mechanical stability of the stainless steel macrostructure, and the presence of accessible Al(OH)x sites. This research shows a clear contribution to sustainability based on multi-factor comparison: The Al-SS catalyst outperforms the state-of-the-art on mechanical and chemical durability, it is both PGM-free and CRM-free, and its preparation follows a simple, scalable and low-waste procedure., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Immobilizing molecular catalysts on electrodes is vital for electrochemical applications. However, creating robust electrode-catalyst interactions while maintaining good catalytic performance and rapid electron transfer is challenging. Here, without introducing any foreign elements, we show a bottom-up synthetic approach of constructing the conjugated C-C bond between the commercial Vulcan carbon electrode and an organometallic catalyst. Characterization results from FTIR, XPS, aberration-corrected TEM and EPR confirmed the successful and uniform heterogenization of the complex. The synthesized Vulcan-LN 4 -Co catalyst is highly active and selective in the oxygen reduction reaction in neutral media, showing an 80 % hydrogen peroxide selectivity and a 0.72 V (vs. RHE) onset potential which significantly outperformed the homogenous counterpart. Based on single-crystal XRD and NMR data, we built a model for density functional theory calculations which showed a nearly optimal binding energy for the *OOH intermediate. Our results show that the direct conjugated C-C bonding is an effective approach for heterogenizing molecular catalysts on carbon, opening new opportunities for employing molecular catalysts in electrochemical applications., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Plastics are ubiquitous in our society. They are in our phones, clothes, bottles, and cars. Yet having improved our lives considerably, they now threaten our environment and our health. The associated carbon emissions and persistency of plastics challenge the fragile balance of many ecosystems. One solution is using biodegradable plastics. Ideally, such plastics are easily assimilated by microorganisms and disappear from our environment. This can help reduce the problems of climate change, microplastics, and littering. However, biodegradable plastics are still only a tiny portion of the global plastics market and require further efforts in research and commercialization. Here, a critical overview of the state of the art of biodegradable plastics is given. Using a material flow analysis, the challenges of the plastic market are highlighted, and with it the large market potential of biodegradable plastics. The environmental and socio-economic impact of plastics, government policies, standards and certifications, physico-chemical properties, and analytical techniques are covered. The Review concludes with a personal outlook on the future of bioplastics, based on our own experience with their development and commercialization., (© 2020 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

MAX (M n+1 AX n ) phases are layered carbides or nitrides with a high thermal and mechanical bulk stability. Recently, it was shown that their surface structure can be modified to form a thin non-stoichiometric oxide layer, which can catalyze the oxidative dehydrogenation of butane. Here, the use of a Ti 2 AlC MAX phase as a support for cobalt oxide was explored for the dry reforming of butane with CO 2 , comparing this new catalyst to more traditional materials. The catalyst was active and selective to synthesis gas. Although the surface structure changed during the reaction, the activity remained stable. Under the same conditions, a titania-supported cobalt oxide catalyst gave low activity and stability due to the agglomeration of cobalt oxide particles. The Co 3 O 4 /Al 2 O 3 catalyst was active, but the acidic surface led to a faster deactivation. The less acidic surface of the Ti 2 AlC was better at inhibiting coke formation. Thanks to their thermal stability and acid-base properties, MAX phases are promising supports for CO 2 conversion reactions., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

One of the main initiatives for fighting climate change is to use carbon dioxide as a resource instead of waste. In this respect, thermocatalytic carbon dioxide hydrogenation to high-added-value chemicals is a promising process. Among the products of this reaction (alcohols, alkanes, olefins, or aromatics), light olefins are interesting because they are building blocks for making polymers, as well as other important chemicals. Olefins are mainly produced from fossil fuel sources, but the increasing demand of plastics boosts the need to develop more sustainable synthetic routes. This review gives a critical overview of the most recent achievements in direct carbon dioxide hydrogenation to light olefins, which can take place through two competitive routes: the modified Fischer-Tropsch synthesis and methanol-mediated synthesis. Both routes are compared in terms of catalyst development, reaction performance, and reaction mechanisms. Furthermore, practical aspects of the commercialization of this reaction, such as renewable hydrogen production and carbon dioxide capture, compression, and transport, are discussed. It is concluded that, to date, the catalysts used in the carbon dioxide hydrogenation reaction give a wide product distribution, which reduces the specific selectivity to lower olefins. More efforts are needed to reach better control of the C/H surface ratio and interactions within the functionalities of the catalyst, as well as understanding the reaction mechanism and avoiding deactivation. Renewable H 2 production and carbon dioxide capture and transport technologies are being developed, although they are currently still too expensive for industrial application., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this short critical perspective, we outline the serious problems caused by air pollution in Europe. Using two types of metrics, level assessment and trend assessment, we quantify the contribution of ammonia, NO x , SO x , non-methane volatile organic compounds, and particulate matter in terms of years of life lost per capita and explain the connection between the various pollutants and their effects on human health and the environment. This is done on the basis of data collected by individual European Union (EU) member states as well as by the EU as a whole. We examine general emission trends as well as sector-specific emissions and discuss the effectiveness of current legislation in reducing health risks and environmental damage. By combining these results with a cost-benefit analysis, we show that a further reduction in NO x emissions is the most urgent and potentially the most beneficial., (© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Petrochemical refineries must separate hydrocarbon mixtures on a large scale for the production of fuels and chemicals. Typically, these hydrocarbons are separated by distillation, which is extremely energy intensive. This high energy cost can be mitigated by developing materials that can enable efficient adsorptive separation. In this critical review, the principles of adsorptive separation are outlined, and then the case for C 4 separations by using zeolites and metal-organic frameworks (MOFs) is examined. By analyzing both experimental and theoretical studies, the challenges and opportunities in C 4 separation are outlined, with a focus on the separation mechanisms and structure-selectivity correlations. Zeolites are commonly used as adsorbents and, in some cases, can separate C 4 mixtures well. The pore sizes of eight-membered-ring zeolites, for example, are in the order of the kinetic diameters of C 4 isomers. Although zeolites have the advantage of a rigid and highly stable structure, this is often difficult to functionalize. MOFs are attractive candidates for hydrocarbon separation because their pores can be tailored to optimize the adsorbate-adsorbent interactions. MOF-5 and ZIF-7 show promising results in separating all C 4 isomers, but breakthrough experiments under industrial conditions are needed to confirm these results. Moreover, the flexibility of the MOF structures could hamper their application under industrial conditions. Adsorptive separation is a promising viable alternative and it is likely to play an increasingly important role in tomorrow's refineries., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The specific capacitance of a highly porous, nitrogen-doped carbon is nearly tripled by orthogonal optimization of the microstructure and surface chemistry. First, the carbons' hierarchical pore structure and specific surface area were tweaked by controlling the temperature and sequence of the thermal treatments. The best process (pyrolysis at 900 °C, washing, and subsequent annealing at 1000 °C) yielded a carbon with a specific capacitance of 117 F g -1 -nearly double that of a carbon made by a typical single-step synthesis at 700 °C. Following the structural optimization, the surface chemistry of the carbons was enriched by applying an oxidation routine based on a mixture of nitric and sulfuric acid in a 1:4 ratio at two different treatment temperatures (0 and 20 °C) and different treatment times. The optimal treatment times were 4 h at 0 °C and only 1 h at 20 °C. Overall, the specific capacitance nearly tripled relative to the original carbon, reaching 168 F g -1 . The inherent nitrogen doping of the carbon comes into interplay with the acid-induced surface functionalization, creating a mixture of oxygen- and nitrogen-oxygen functionalities. The evolution of the surface chemistry was carefully followed by X-ray photoelectron spectroscopy and by N 2 sorption porosimetry, revealing stepwise surface functionalization and simultaneous carbon etching. Overall, these processes are responsible for the peak-shaped capacitance trends in the carbons., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We introduce the concept of using site-specific sulfation of various lignins for increasing their aqueous solubility and thereby their processability. Using p-nitrophenylsulfate as a sulfate source and an aryl sulfotransferase enzyme as catalyst, lignins are easily sulfated at ambient conditions. We demonstrate the specific sulfation of phenolic hydroxyl groups on five different lignins: Indulin AT (Kraft softwood), Protobind 1000 (mixed wheat straw/Sarkanda grass soda) and three organosolv lignins. The reaction proceeds smoothly and the increase in solubility is visible to the naked eye. We then examine the reaction kinetics, and show that these are easily monitored qualitatively and quantitatively using UV/Vis spectroscopy. The UV/Vis results are validated with 31 P NMR spectroscopy of the lignin phenol groups after derivatization with phosphorylation reagent II. In general, the results are more significant with organosolv lignins, as Kraft and soda lignins are produced from aqueous lignocellulose extraction processes., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We explored the depolymerisation of several lignins in liquid ammonia at relatively high temperatures and pressures (120 °C and 88 bar). Five different lignins were tested: Indulin AT kraft, Protobind 1000 soda, wheat straw organosolv, poplar organosolv and elephant grass-milled wood lignin (EG MWL). In pure liquid ammonia, all lignins underwent slow incorporation of nitrogen into their structure, resulting in higher molecular weight and polydispersity index. Subsequently, we show a reductive depolymerisation by solvated electrons at room temperature by adding sodium metal to the liquid ammonia without any external hydrogen donor. The netto yields of bio-oil are low for technical lignins (10-23 %), but with higher yields of alkylphenols. In the case of native EG MWL, netto yields of 40 % bio-oil were achieved. Finally, when the room temperature method was applied to poplar wood fibre, we observe improved delignification upon the addition of sodium compared to poplar wood fractionation in pure liquid ammonia., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We study the catalytic condensation of furfuryl alcohol with 1-butanol to butyl levulinate. A screening of several commercial and as-synthesized solid acid catalysts shows that propylsulfonic acid-functionalized mesoporous silica outperforms the state-of-the-art phosphotungstate acid catalysts. The catalyst is prepared via template-assisted sol-gel polycondensation of TEOS and MPTMS. It gives 96 % yield (and 100 % selectivity) of butyl levulinate in 4 h at 110 °C. Reaction profiles before and after a hot filtration test confirm that the active catalytic species do not leach into the solution. The catalyst synthesis, characterization, and mode of operation are presented and discussed., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)