Atomic‐Level Reactive Sites for Semiconductor‐Based Photocatalytic CO2 Reduction

Photocatalytic CO₂ reduction is an effective means to generate renewable energy. It involves redox reactions, reduction of CO₂ and oxidation of water, that leads to the production of solar fuel. Significant research effort has therefore been made to develop inexpensive and practically sustainable semiconductor‐based photocatalysts. The exploration of atomic‐level active sites on the surface of semiconductors can result in an improved understanding of the mechanism of CO₂ photoreduction. This can be applied to the design and synthesis of efficient photocatalysts. In this review, atomic‐level reactive sites are classified into four types: vacancies, single atoms, surface functional groups, and frustrated Lewis pairs (FLPs). These different photocatalytic reactive sites are shown to have varied affinity to reactants, intermediates, and products. This changes pathways for CO₂ reduction and significantly impacts catalytic activity and selectivity. The design of a photocatalyst from an atomic‐level perspective can therefore be used to maximize atomic utilization efficiency and lead to a high selectivity. The prospects for fabrication of effective photocatalysts based on an in‐depth understanding are highlighted.     

Electrocatalytic Reduction of Gaseous CO2 to CO on Sn/Cu‐Nanofiber‐Based Gas Diffusion Electrodes

Earth‐abundant Sn/Cu catalysts are highly selective for the electrocatalytic reduction of CO₂ to CO in aqueous electrolytes. However, CO₂ mass transport limitations, resulting from the low solubility of CO₂ in water, so far limit the CO partial current density for Sn/Cu catalysts to about 10 mA cm^?2. Here, a freestanding gas diffusion electrode design based on Sn‐decorated Cu‐coated electrospun polyvinylidene fluoride nanofibers is demonstrated. The use of gaseous CO₂ as a feedstock alleviates mass transport limitations, resulting in high CO partial current densities above 100 mA cm^?2, while maintaining high CO faradaic efficiencies above 80%. These results represent an important step toward an economically viable pathway to CO₂ reduction.     

Electrochemical CO2 Reduction with Atomic Iron‐Dispersed on Nitrogen‐Doped Graphene

Electrochemical reduction of CO₂ provides an opportunity to reach a carbon‐neutral energy recycling regime, in which CO₂ emissions from fuel use are collected and converted back to fuels. The reduction of CO₂ to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for CO₂ conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO₂ reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The CO₂ reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N₄) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.     

Nitrogen‐mediated effects of elevated CO2 on intra‐aggregate soil pore structure

Soil pore structure has a strong influence on water retention, and is itself influenced by plant and microbial dynamics such as root proliferation and microbial exudation. Although increased nitrogen (N) availability and elevated atmospheric CO₂ concentrations (eCO₂) often have interacting effects on root and microbial dynamics, it is unclear whether these biotic effects can translate into altered soil pore structure and water retention. This study was based on a long‐term experiment (7 yr at the time of sampling) in which a C₄ pasture grass (Paspalum notatum) was grown on a sandy loam soil while provided factorial additions of N and CO₂. Through an analysis of soil aggregate fractal properties supported by 3D microtomographic imagery, we found that N fertilization induced an increase in intra‐aggregate porosity and a simultaneous shift toward greater accumulation of pore space in larger aggregates. These effects were enhanced by eCO₂ and yielded an increase in water retention at pressure potentials near the wilting point of plants. However, eCO₂ alone induced changes in the opposite direction, with larger aggregates containing less pore space than under control conditions, and water retention decreasing accordingly. Results on biotic factors further suggested that organic matter gains or losses induced the observed structural changes. Based on our results, we postulate that the pore structure of many mineral soils could undergo N‐dependent changes as atmospheric CO₂ concentrations rise, having global‐scale implications for water balance, carbon storage, and related rhizosphere functions.     

Jasmonate‐mediated stomatal closure under elevated CO2 revealed by time‐resolved metabolomics

Foliar stomatal movements are critical for regulating plant water loss and gas exchange. Elevated carbon dioxide (CO₂) levels are known to induce stomatal closure. However, the current knowledge on CO₂ signal transduction in stomatal guard cells is limited. Here we report metabolomic responses of Brassica napus guard cells to elevated CO₂ using three hyphenated metabolomics platforms: gas chromatography‐mass spectrometry (MS); liquid chromatography (LC)‐multiple reaction monitoring‐MS; and ultra‐high‐performance LC‐quadrupole time‐of‐flight‐MS. A total of 358 metabolites from guard cells were quantified in a time‐course response to elevated CO₂ level. Most metabolites increased under elevated CO₂, showing the most significant differences at 10 min. In addition, reactive oxygen species production increased and stomatal aperture decreased with time. Major alterations in flavonoid, organic acid, sugar, fatty acid, phenylpropanoid and amino acid metabolic pathways indicated changes in both primary and specialized metabolic pathways in guard cells. Most interestingly, the jasmonic acid (JA) biosynthesis pathway was significantly altered in the course of elevated CO₂ treatment. Together with results obtained from JA biosynthesis and signaling mutants as well as CO₂ signaling mutants, we discovered that CO₂‐induced stomatal closure is mediated by JA signaling.     

High‐solids biphasic CO2–H2O pretreatment of lignocellulosic biomass

A high pressure (200 bar) CO₂–H₂O process was developed for pretreating lignocellulosic biomass at high‐solid contents, while minimizing chemical inputs. Hardwood was pretreated at 20 and 40 (wt.%) solids. Switchgrass, corn stover, big bluestem, and mixed perennial grasses (a co‐culture of big bluestem and switchgrass) were pretreated at 40 (wt.%) solids. Operating temperatures ranged from 150 to 250°C, and residence times from 20 s to 60 min. At these conditions a biphasic mixture of an H₂O‐rich liquid (hydrothermal) phase and a CO₂‐rich supercritical phase coexist. Following pretreatment, samples were then enzymatically hydrolyzed. Total yields, defined as the fraction of the theoretical maximum, were determined for glucose, hemicellulose sugars, and two degradation products: furfural and 5‐hydroxymethylfurfural. Response surfaces of yield as a function of temperature and residence time were compared for different moisture contents and biomass species. Pretreatment at 170°C for 60 min gave glucose yields of 77%, 73%, and 68% for 20 and 40 (wt.%) solids mixed hardwood and mixed perennial grasses, respectively. Pretreatment at 160°C for 60 min gave glucan to glucose yields of 81% for switchgrass and 85% for corn stover. Biotechnol. Bioeng. 2010;107: 451–460. © 2010 Wiley Periodicals, Inc.     

Lower‐than‐expected CH4 emissions from rice paddies with rising CO2 concentrations

Elevated atmospheric CO₂ (eCO₂) generally increases carbon input in rice paddy soils and stimulates the growth of methane‐producing microorganisms. Therefore, eCO₂ is widely expected to increase methane (CH₄) emissions from rice agriculture, a major source of anthropogenic CH₄. Agricultural practices strongly affect CH₄ emissions from rice paddies as well, but whether these practices modulate effects of eCO₂ is unclear. Here we show, by combining a series of experiments and meta‐analyses, that whereas eCO₂ strongly increased CH₄ emissions from paddies without straw incorporation, it tended to reduce CH₄ emissions from paddy soils with straw incorporation. Our experiments also identified the microbial processes underlying these results: eCO₂ increased methane‐consuming microorganisms more strongly in soils with straw incorporation than in soils without straw, with the opposite pattern for methane‐producing microorganisms. Accounting for the interaction between CO₂ and straw management, we estimate that eCO₂ increases global CH₄ emissions from rice paddies by 3.7%, an order of magnitude lower than previous estimates. Our results suggest that the effect of eCO₂ on CH₄ emissions from rice paddies is smaller than previously thought and underline the need for judicious agricultural management to curb future CH₄ emissions.     

Fate of xylem‐transported 11C‐ and 13C‐labeled CO2 in leaves of poplar

In recent studies, assimilation of xylem‐transported CO₂ has gained considerable attention as a means of recycling respired CO₂ in trees. However, we still lack a clear and detailed picture on the magnitude of xylem‐transported CO₂ assimilation, in particular within leaf tissues. To this end, detached poplar leaves (Populus × canadensis Moench ‘Robusta’) were allowed to take up a dissolved ¹³CO₂ label serving as a proxy of xylem‐transported CO₂ entering the leaf from the branch. The uptake rate of the ¹³C was manipulated by altering the vapor pressure deficit (VPD) (0.84, 1.29 and 1.83 kPa). Highest tissue enrichments were observed under the highest VPD. Among tissues, highest enrichment was observed in the petiole and the veins, regardless of the VPD treatment. Analysis of non‐labeled leaves showed that some ¹³C diffused from the labeled leaves and was fixed in the mesophyll of the non‐labeled leaves. However, ¹³C leaf tissue enrichment analysis with elemental analysis coupled to isotope ratio mass spectrometry was limited in spatial resolution at the leaf tissue level. Therefore, ¹¹C‐based CO₂ labeling combined with positron autoradiography was used and showed a more detailed spatial distribution within a single tissue, in particular in secondary veins. Therefore, in addition to ¹³C, ¹¹C‐based autoradiography can be used to study the fate of xylem‐transported CO₂ at leaf level, allowing the acquisition of data at a yet unprecedented resolution.     

Terrestrial biosphere model performance for inter‐annual variability of land‐atmosphere CO2 exchange

Interannual variability in biosphere‐atmosphere exchange of CO₂ is driven by a diverse range of biotic and abiotic factors. Replicating this variability thus represents the ‘acid test’ for terrestrial biosphere models. Although such models are commonly used to project responses to both normal and anomalous variability in climate, they are rarely tested explicitly against inter‐annual variability in observations. Herein, using standardized data from the North American Carbon Program, we assess the performance of 16 terrestrial biosphere models and 3 remote sensing products against long‐term measurements of biosphere‐atmosphere CO₂ exchange made with eddy‐covariance flux towers at 11 forested sites in North America. Instead of focusing on model‐data agreement we take a systematic, variability‐oriented approach and show that although the models tend to reproduce the mean magnitude of the observed annual flux variability, they fail to reproduce the timing. Large biases in modeled annual means are evident for all models. Observed interannual variability is found to commonly be on the order of magnitude of the mean fluxes. None of the models consistently reproduce observed interannual variability within measurement uncertainty. Underrepresentation of variability in spring phenology, soil thaw and snowpack melting, and difficulties in reproducing the lagged response to extreme climatic events are identified as systematic errors, common to all models included in this study.     

Canopy radiation‐ and water‐use efficiencies as affected by elevated [CO2]

This study used an environmentally controlled plant growth facility, EcoCELLs, to measure canopy gas exchanges directly and to examine the effects of elevated [CO₂] on canopy radiation‐ and water‐use efficiencies. Sunflowers (Helianthus annus var. Mammoth) were grown at ambient (399 μmol mol^?1) and elevated [CO₂] (746 μmol mol^?1) for 53 days in EcoCELLs. Whole canopy carbon‐ and water‐fluxes were measured continuously during the period of the experiment. The results indicated that elevated [CO₂] enhanced daily total canopy carbon‐ and water‐fluxes by 53% and 11%, respectively, on a ground‐area basis, resulting in a 54% increase in radiation‐use efficiency (RUE) based on intercepted photosynthetic active radiation and a 26% increase in water‐use efficiency (WUE) by the end of the experiment. Canopy carbon‐ and water‐fluxes at both CO₂ treatments varied with canopy development. They were small at 22 days after planting (DAP) and gradually increased to the maxima at 46 DAP. When canopy carbon‐ and water‐fluxes were expressed on a leaf‐area basis, no effect of CO₂ was found for canopy water‐flux while elevated [CO₂] still enhanced canopy carbon‐flux by 29%, on average. Night‐time canopy carbon‐flux was 32% higher at elevated than at ambient [CO₂]. In addition, RUE and WUE displayed strong diurnal variations, high at noon and low in the morning or afternoon for WUE but opposite for RUE. This study provided direct evidence that plant canopy may consume more, instead of less, water but utilize both water and radiation more efficiently at elevated than at ambient [CO₂], at least during the exponential growth period as illustrated in this experiment.     

Manganese Oxide Modified Nickel Catalysts for Photothermal CO Hydrogenation to Light Olefins

Ni‐based catalysts are traditionally considered unsuitable for the Fischer–Tropsch syntheses of olefins, due to the very strong hydrogenation ability of metallic Ni. Herein, this paradigm is challenged. A series of MnO supports nickel catalysts (denoted herein as Ni‐x) are fabricated by H₂ reduction of a nickel‐manganese mixed metal oxide at temperatures (x) ranging from 250 to 600 °C. The Ni‐500 catalyst displays unprecedented performance for photothermal CO hydrogenation to olefins, with an olefin selectivity of 33.0% under ultraviolet–visible irradiation. High‐resolution transmission electron microscopy, X‐ray absorption spectroscopy (XAS), and X‐ray diffraction analyses reveal that the Ni‐x catalysts contain metallic Ni nanoparticles supported by MnO. X‐ray photoelectron spectroscopy and XAS establish that electron transfer from MnO to the Ni⁰ nanoparticles is responsible for modifying the electronic structure of nickel (creating Ni^δ? states), thereby shifting the CO hydrogenation selectivity toward light olefins. Further, density functional theory calculations show that this electron transfer lowers the adsorption energies of olefins on Ni surfaces, thus minimizing the undesirable deep hydrogenation reactions to higher alkanes. This study conclusively demonstrates that MnO‐modified Ni‐based catalyst systems can be highly selective for CO hydrogenation to light olefins.     

Strong overestimation of water‐use efficiency responses to rising CO2 in tree‐ring studies

The carbon isotope ratio (δ¹³C) in tree rings is commonly used to derive estimates of the assimilation‐to‐stomatal conductance rate of trees, that is, intrinsic water‐use efficiency (iWUE). Recent studies have observed increased iWUE in response to rising atmospheric CO₂ concentrations (C_a), in many different species, genera and biomes. However, increasing rates of iWUE vary widely from one study to another, likely because numerous covarying factors are involved. Here, we quantified changes in iWUE of two widely distributed boreal conifers using tree samples from a forest inventory network that were collected across a wide range of growing conditions (assessed using the site index, SI), developmental stages and stand histories. Using tree‐ring isotopes analysis, we assessed the magnitude of increase in iWUE after accounting for the effects of tree size, stand age, nitrogen deposition, climate and SI. We also estimated how growth conditions have modulated tree physiological responses to rising C_a. We found that increases in tree size and stand age greatly influenced iWUE. The effect of C_a on iWUE was strongly reduced after accounting for these two variables. iWUE increased in response to C_a, mostly in trees growing on fertile stands, whereas iWUE remained almost unchanged on poor sites. Our results suggest that past studies could have overestimated the CO₂ effect on iWUE, potentially leading to biased inferences about the future net carbon balance of the boreal forest. We also observed that this CO₂ effect is weakening, which could affect the future capacity of trees to resist and recover from drought episodes.     

The CO2‐equivalent balance of freshwater ecosystems is non‐linearly related to productivity

Eutrophication of fresh waters results in increased CO₂ uptake by primary production, but at the same time increased emissions of CH₄ to the atmosphere. Given the contrasting effects of CO₂ uptake and CH₄ release, the net effect of eutrophication on the CO₂‐equivalent balance of fresh waters is not clear. We measured carbon fluxes (CO₂ and CH₄ diffusion, CH₄ ebullition) and CH₄ oxidation in 20 freshwater mesocosms with 10 different nutrient concentrations (total phosphorus range: mesotrophic 39 µg/L until hypereutrophic 939 µg/L) and planktivorous fish in half of them. We found that the CO₂‐equivalent balance had a U‐shaped relationship with productivity, up to a threshold in hypereutrophic systems. CO₂‐equivalent sinks were confined to a narrow range of net ecosystem production (NEP) between 5 and 19 mmol O₂ m^?3 day^?1. Our findings indicate that eutrophication can shift fresh waters from sources to sinks of CO₂‐equivalents due to enhanced CO₂ uptake, but continued eutrophication enhances CH₄ emission and transforms freshwater ecosystems to net sources of CO₂‐equivalents to the atmosphere. Nutrient enrichment but also planktivorous fish presence increased productivity, thereby regulating the resulting CO₂‐equivalent balance. Increasing planktivorous fish abundance, often concomitant with eutrophication, will consequently likely affect the CO₂‐equivalent balance of fresh waters.     

Causes of slowing‐down seasonal CO2 amplitude at Mauna Loa

Changing amplitude of the seasonal cycle of atmospheric CO₂ (SCA) in the northern hemisphere is an emerging carbon cycle property. Mauna Loa (MLO) station (20°N, 156°W), which has the longest continuous northern hemisphere CO₂ record, shows an increasing SCA before the 1980s (p < .01), followed by no significant change thereafter. We analyzed the potential driving factors of SCA slowing‐down, with an ensemble of dynamic global vegetation models (DGVMs) coupled with an atmospheric transport model. We found that slowing‐down of SCA at MLO is primarily explained by response of net biome productivity (NBP) to climate change, and by changes in atmospheric circulations. Through NBP, climate change increases SCA at MLO before the 1980s and decreases it afterwards. The effect of climate change on the slowing‐down of SCA at MLO is mainly exerted by intensified drought stress acting to offset the acceleration driven by CO₂ fertilization. This challenges the view that CO₂ fertilization is the dominant cause of emergent SCA trends at northern sites south of 40°N. The contribution of agricultural intensification on the deceleration of SCA at MLO was elusive according to land–atmosphere CO₂ flux estimated by DGVMs and atmospheric inversions. Our results also show the necessity to adequately account for changing circulation patterns in understanding carbon cycle dynamics observed from atmospheric observations and in using these observations to benchmark DGVMs.