The environmental sustainability of digital content consumption.

Internet access has reached 60% of the global population, with the average user spending over 40% of their waking life on the Internet, yet the environmental implications remain poorly understood. Here, we assess the environmental impacts of digital content consumption in relation to the Earth's carrying capacity, finding that currently the global average consumption of web surfing, social media, video and music streaming, and video conferencing could account for approximately 40% of the per capita carbon budget consistent with limiting global warming to 1.5 °C, as well as around 55% of the per capita carrying capacity for mineral and metal resources use and over 10% for five other impact categories. Decarbonising electricity would substantially mitigate the climate impacts linked to Internet consumption, while the use of mineral and metal resources would remain of concern. A synergistic combination of rapid decarbonisation and additional measures aimed at reducing the use of fresh raw materials in electronic devices (e.g., lifetime extension) is paramount to prevent the growing Internet demand from exacerbating the pressure on the finite Earth's carrying capacity.

Aiming for More Sustainable Cross-Coupling Chemistry by Employing Single-Atom Catalysis on Scale.

Scaling up syntheses from mg to kg quantities is a complex endeavor. Besides adapting laboratory protocols to industrial processes and equipment and thorough safety assessments, much attention is paid to the reduction of the process' environmental impact. For processes including transition metal catalyzed steps, e.g. cross-coupling chemistry, this impact strongly depends on the identity of the metal used. As such, a key approach is the replacement of single-use with reusable heterogeneous catalysts. Transition metal single-atom heterogeneous catalysts (SAC), a novel class of catalytic materials, might exhibit all the necessary properties to step up to this task. This article shall discuss current applications of SAC in cross-coupling chemistry from the point of a process chemist and shed light on the NCCR Catalysis contribution to the field. Investigations of the stability-activity-selectivity relationship of SACs in combination with early-stage life-cycle assessments (LCA) of potential processes lay the foundation for large-scale application tailored catalyst synthesis. Ultimately, prevailing challenges are highlighted, which need to be addressed in future research.

Geminal-atom catalysis for cross-coupling.

Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis1-4. However, the architecture of these mononuclear metal species stabilized on solid supports may not be optimal for catalysing complex molecular transformations owing to restricted spatial environment and electronic quantum states5,6. Here we report a class of heterogeneous geminal-atom catalysts (GACs), which pair single-atom sites in specific coordination and spatial proximity. Regularly separated nitrogen anchoring groups with delocalized π-bonding nature in a polymeric carbon nitride (PCN) host7 permit the coordination of Cu geminal sites with a ground-state separation of about 4 Å at high metal density8. The adaptable coordination of individual Cu sites in GACs enables a cooperative bridge-coupling pathway through dynamic Cu-Cu bonding for diverse C-X (X = C, N, O, S) cross-couplings with a low activation barrier. In situ characterization and quantum-theoretical studies show that such a dynamic process for cross-coupling is triggered by the adsorption of two different reactants at geminal metal sites, rendering homo-coupling unfeasible. These intrinsic advantages of GACs enable the assembly of heterocycles with several coordination sites, sterically congested scaffolds and pharmaceuticals with highly specific and stable activity. Scale-up experiments and translation to continuous flow suggest broad applicability for the manufacturing of fine chemicals.

Microalgae Biofuel for a Heavy-Duty Transport Sector within Planetary Boundaries.

In this contribution, we study the extent to which 68 scenarios for microalgae biofuels could help the heavy-duty transport sector operate within planetary boundaries. The proposed scenarios are built considering a range of alternative configurations based on three types of fuel production processes (i.e., transesterification, hydrodeoxygenation, and hydrothermal liquefaction), different carbon sources (such as natural gas power plants and direct air capture), byproduct treatments, and two electricity mixes. Our results reveal that microalgae biofuels could significantly reduce the environmental and human health impacts of the business-as-usual (fossil-based) heavy-duty transport sector. Moreover, relative to standard biofuels that show large land-use requirements, we find that microalgae biofuels also decrease the damage on biosphere integrity substantially. Notably, pathways resorting to hydrodeoxygenation of microalgae oil and direct air capture and carbon storage could reduce the current impact induced globally on climate change by the heavy transport by 77%, while attaining six-fold reductions in biosphere integrity impacts, both relative to conventional biofuels.

Absolute environmental sustainability assessment of renewable dimethyl ether fuelled heavy-duty trucks.

In recent years, liquid fuels from renewable carbon that can replace fossil ones with minimal infrastructure changes have attracted increasing interest in decarbonising the heavy-duty long-haul sector. Here we focus on dimethyl ether (DME), a promising alternative to diesel due to its high cetane number, oxygen content, and more efficient and cleaner propulsion that results in low particulate matter and sulphur oxide emissions. Going well beyond previous studies that quantified the environmental impact of DME, often in terms of global warming, here we evaluate DME use in heavy-duty trucks in the context of seven planetary boundaries, all essential for maintaining the Earth's stability. Focusing on several scenarios differing in the feedstock origin, we find that routes based on fossil carbon, either in the form of coal, natural gas, or captured CO2 from fossil plants, would increase the greenhouse gas emissions relative to the business-as-usual. Only scenarios based on renewable carbon could reduce the impacts on climate change, while hydrogen from biomass gasification coupled with carbon capture and storage (CCS) and DME from biomass gasification with CCS could enable an environmentally sustainable operation within all the planetary boundaries. Overall, our work opens up new avenues for the environmental assessment of fuels considering the finite capacity of the Earth system to guide research and policy-making more sensibly.

Human and planetary health implications of negative emissions technologies.

Meeting the 1.5 °C target may require removing up to 1,000 Gtonne CO2 by 2100 with Negative Emissions Technologies (NETs). We evaluate the impacts of Direct Air Capture and Bioenergy with Carbon Capture and Storage (DACCS and BECCS), finding that removing 5.9 Gtonne/year CO2 can prevent <9·102 disability-adjusted life years per million people annually, relative to a baseline without NETs. Avoiding this health burden-similar to that of Parkinson's-can save substantial externalities (≤148 US$/tonne CO2), comparable to the NETs levelized costs. The health co-benefits of BECCS, dependent on the biomass source, can exceed those of DACCS. Although both NETs can help to operate within the climate change and ocean acidification planetary boundaries, they may lead to trade-offs between Earth-system processes. Only DACCS can avert damage to the biosphere integrity without challenging other biophysical limits (impacts ≤2% of the safe operating space). The quantified NETs co-benefits can incentivize their adoption.

The role of hydrogen in heavy transport to operate within planetary boundaries.

Green hydrogen, i.e., produced from renewable resources, is attracting attention as an alternative fuel for the future of heavy road transport and long-distance driving. However, the benefits linked to zero pollution at the usage stage can be overturned when considering the upstream processes linked to the raw materials and energy requirements. To better understand the global environmental implications of fuelling heavy transport with hydrogen, we quantified the environmental impacts over the full life cycle of hydrogen use in the context of the Planetary Boundaries (PBs). The scenarios assessed cover hydrogen from biomass gasification (with and without carbon capture and storage [CCS]) and electrolysis powered by wind, solar, bioenergy with CCS, nuclear, and grid electricity. Our results show that the current diesel-based-heavy transport sector is unsustainable due to the transgression of the climate change-related PBs (exceeding standalone by two times the global climate-change budget). Hydrogen-fuelled heavy transport would reduce the global pressure on the climate change-related PBs helping the transport sector to stay within the safe operating space (i.e., below one-third of the global ecological budget in all the scenarios analysed). However, the best scenarios in terms of climate change, which are biomass-based, would shift burdens to the biosphere integrity and nitrogen flow PBs. In contrast, burden shifting in the electrolytic scenarios would be negligible, with hydrogen from wind electricity emerging as an appealing technology despite attaining higher carbon emissions than the biomass routes.

Planetary metrics for the absolute environmental sustainability assessment of chemicals.

Environmental assessments in green chemistry often rely on simplified metrics that enable comparisons between alternative routes but fail to shed light on whether they are truly sustainable in absolute terms, viz. relative to the Earth's ecological capacity. To expand our currently limited knowledge of the extent to which chemicals are environmentally sustainable, here we analyse 492 chemical products through the lens of seven planetary boundaries representing critical biophysical limits that should never be exceeded. We found that most of them transgress these environmental guardrails, mainly the ones strongly connected to greenhouse gas emissions (i.e., climate change, ocean acidification and biosphere integrity). However, their levels of transgression fail to correlate with their carbon footprints, currently the focus of most studies, implying that chemicals entailing higher greenhouse gas emissions are not necessarily less environmentally sustainable in absolute terms. Our work points towards the need to embrace absolute sustainability criteria in current environmental assessments, which will require agreeing on how to allocate shares of the planet's ecological capacity among anthropogenic activities, including chemicals' production. This work's absolute environmental sustainability assessment (AESA) method, which could complement standard life cycle assessment approaches, might help experimental researchers working in green chemistry develop truly 'green' products. The AESA method should be taken as a starting point to devise holistic approaches for quantifying the absolute environmental impact of chemicals to guide research and policymaking more sensibly.