Anthropogenic Carbon Research Articles

Agricultural carbon emissions in China: measurement, spatiotemporal evolution, and influencing factors analysis

IntroductionThe agricultural sector is the second largest emitter of greenhouse gases, accounting for 23% of global anthropogenic carbon emissions. Analysis of the basic state of carbon emissions from China's agriculture is helpful to achieve carbon reduction targets.MethodsAgricultural carbon emissions were calculated using the emission factor method, based on data from the China Rural Statistical Yearbook and various provincial statistical yearbooks. To analyze spatial patterns, the standard deviation ellipse method and the center of gravity migration model were employed, uncovering the migration path of agricultural carbon emissions. Regional disparities and the driving factors of agricultural carbon emissions were further examined using the Theil index and the Logarithmic Mean Divisia Index (LMDI) model.ResultsThe analysis indicated that the emissions center has gradually shifted towards the central and western regions, reflecting changes in agricultural production activity areas. Intraregional differences are the primary contributors to the imbalance in agricultural carbon emissions, with pronounced disparities in grain production and consumption balance regions. Key influencing factors include agricultural production efficiency, adjustments in agricultural industrial structure, economic structure and output, and urbanization levels. The economic output effect and urbanization effect are identified as the main drivers of increased carbon emissions, while declining production efficiency has hindered emission reduction efforts.ConclusionThe findings provide valuable insights for regional management and policymaking in China's agricultural sector, highlighting the need to enhance production efficiency and optimize agricultural structure to reduce emissions.

Nickel-Doped Facet-Selective Copper Nanowires for Activating CO-to-Ethanol Electrosynthesis.

Ethanol isa promising energy vector for closing the anthropogenic carbon cycle through reversible electrochemical redox. Currently, ethanol electrosynthesissuffers from low product selectivity due to the competitive advantage of ethylene in CO2/CO electroreduction. Here, a facet-selective metal-doping strategy is reported, tuning the reaction kinetics of CO reduction paths and thus enhancing the ethanol selectivity. The theoretical calculations reveal that nickel (Ni)doped Cu(100) surface facilitates water dissociation to form adsorbed hydrogen, which promotesselective electrochemical hydrogenation of a key C2 intermediate (*CHCOH) toward ethanol path over ethylene path. Experimentally, a solution-phase synthesis of a Ni-doped {100}-dominated Copper nanowires (Cu NWs) catalyst is reported, enabling an ethanol Faradaic efficiency of 56% and a selectivity ratio of ethanol to ethylene of 2.7, which are ≈4 and 15 times larger than those of undoped Cu NWs, respectively. The operando spectroscopic characterizationsconfirm that Ni-doping in Cu NWs can alter the interfacial water activity and thus regulate the C2 product selectivity. With further electrode engineering, a membrane electrode assembly electrolyzer using Ni-doped Cu NWs catalysts demonstrates an ethanol Faradaic efficiency over 50% at 300mA cm-2 with a full cell voltage of ≈2.7V and operates stably for over 300 h.

Carbon dioxide and evapotranspiration fluxes in an urban area of Krakow, Poland

AbstractUrban areas play an essential role in the global carbon balance, being responsible for more than 70% of anthropogenic carbon emissions, entering the atmosphere mainly in the form of carbon dioxide (CO2). Another crucial component of the carbon balance of the urban atmosphere is CO2 exchange with the biosphere, expressed in both emission and absorption fluxes. The biosphere component of the net CO2 flux is inseparably linked to the water (H2O) balance due to evapotranspiration. This article presents an estimation of CO2 and H2O net fluxes based on eddy covariance (EC) tower measurements and in‐depth analysis of its temporal and spatial variability for a typical urban site at mid‐latitude of the northern hemisphere. The source area was divided into two sectors, one representing dense urban development with sources of CO2 from traffic and households, and the second containing predominantly recreation and sports areas. Temporal variability analysis of evapotranspiration showed a clear seasonal cycle closely correlated with incoming radiation and air temperature, with the seasonal mean ranging from 0.4 mm·day−1 in winter to 1.6 mm·day−1 in summer. As a result of similar green coverage between the urban and green sectors, spatial variability was statistically insignificant. The net CO2 flux over a seasonal cycle was less pronounced for the total source area with a mean of 5.0 g C·m−2·day−1 in summer and 7.5 g C·m−2·day−1 in winter. However, significant variations between urban and green sectors were observed with the highest seasonal mean difference of 4.5 g C·m−2·day−1 in winter. The results confirm that while on the local, short time‐scale urban vegetation has a potential to mitigate the emissions, it is not able to offset them.

Hydrological cycle amplification imposes spatial patterns on the climate change response of ocean pH and carbonate chemistry

Abstract. ​​​​​​​Ocean CO2 uptake and acidification in response to human activities are driven primarily by the rise in atmospheric CO2 but are also modulated by climate change. Existing work suggests that this “climate effect” influences the uptake and storage of anthropogenic carbon and acidification via the global increase in ocean temperature, although some regional responses have been attributed to changes in circulation or biological activity. Here, we investigate spatial patterns in the climate effect on surface ocean acidification (and the closely related carbonate chemistry) in an Earth system model under a rapid CO2-increase scenario and identify a different driving process. We show that the amplification of the hydrological cycle, a robustly simulated feature of climate change, is largely responsible for the spatial patterns in this climate effect at the sea surface. This “hydrological effect” can be understood as a subset of the total climate effect, which includes warming, hydrological cycle amplification, circulation, and biological changes. We demonstrate that it acts through two primary mechanisms: (i) directly diluting or concentrating dissolved ions by adding or removing freshwater and (ii) altering the sea surface temperature, which influences the solubility of dissolved inorganic carbon (DIC) and acidity of seawater. The hydrological effect opposes acidification in salinifying regions, most notably the subtropical Atlantic, and enhances acidification in freshening regions such as the western Pacific. Its single strongest effect is to dilute the negative ions that buffer the dissolution of CO2, quantified as alkalinity. The local changes in alkalinity, DIC, and pH linked to the pattern of hydrological cycle amplification are as strong as the (largely uniform) changes due to warming, explaining the weak increase in pH and DIC seen in the climate effect in the subtropical Atlantic Ocean.

Enhanced ocean CO2 uptake due to near-surface temperature gradients

AbstractThe ocean annually absorbs about a quarter of all anthropogenic carbon dioxide (CO2) emissions. Global estimates of air–sea CO2 fluxes are typically based on bulk measurements of CO2 in air and seawater and neglect the effects of vertical temperature gradients near the ocean surface. Theoretical and laboratory observations indicate that these gradients alter air–sea CO2 fluxes, because the air–sea CO2 concentration difference is highly temperature sensitive. However, in situ field evidence supporting their effect is so far lacking. Here we present independent direct air–sea CO2 fluxes alongside indirect bulk fluxes collected along repeat transects in the Atlantic Ocean (50° N to 50° S) in 2018 and 2019. We find that accounting for vertical temperature gradients reduces the difference between direct and indirect fluxes from 0.19 mmol m−2 d−1 to 0.08 mmol m−2 d−1 (N = 148). This implies an increase in the Atlantic CO2 sink of ~0.03 PgC yr−1 (~7% of the Atlantic Ocean sink). These field results validate theoretical, modelling and observational-based efforts, all of which predicted that accounting for near-surface temperature gradients would increase estimates of global ocean CO2 uptake. Accounting for this increased ocean uptake will probably require some revision to how global carbon budgets are quantified.

Advances in the understanding of selective CO2 reduction catalysis

AbstractThe electrochemical synthesis for value‐added chemicals and fuels via carbon dioxide reduction reaction (CO2RR) offers an effective route to close the anthropogenic carbon cycle and store renewable energy. Currently, the copper‐based catalyst is still the only choice for generating various CO2RR species beyond two electron products. However, the wide range of CO2RR products generated on copper leads to low selectivity, and their low concentrations in electrolytes pose great costs in the downstream purification process and significantly challenge the scalability of this technology. To make this technology economically viable, enhancing product selectivity is crucial. In this review, we identify the primary CO2RR species and discuss the latest insights into the reaction mechanisms controlling CO2RR selectivity. Then, we examined factors that affect CO2RR selectivity. Emphasizing these factors in catalyst design, we highlight the importance of advanced technologies to expand our knowledge and prospects for the future of the CO2RR.

The carbon crater: Comparing anthropogenic greenhouse gas emissions to historical planetary events

Equilibrium climate sensitivity modeling relies heavily on paleoclimate records that were affected by meteorite impacts and volcanic explosions. This paper conducts a thought experiment by re-assembling known data and theories to shed new light on anthropogenic carbon waste. Anthropogenic activity, meteorite impacts and volcanic explosions all extract material from the Earth’s crust and deposit it in the atmosphere. This thought experiment tests if the mass of anthropogenic greenhouse gas emissions from 1851 to 2021 is comparable to the mass of atmospheric emissions from historical planetary events. Approximately 3.60 trillion tons of anthropogenic carbon dioxide equivalents are converted into volume and then transformed into the shape of a meteorite impact structure named the “Carbon Crater.” The 35 km crater (bounded by 34%–68% confidence intervals of 25–45 km) would rank 23rd on the list of known impact structures. The 2.6 km projectile required to create the Crater would be a 10 on the 1–10 Torino hazard scale described as “. . .capable of causing global climatic catastrophe. . .” The estimated re-occurrence interval for a projectile of this size is 5.3 million years. An interval of this time in Earth’s recent history predates homo sapiens. The Crater’s volume is exponentially larger than the 1883 eruption of Krakatoa and ranks as an 8 (“mega-colossal”) on the 0–8 Volcanic Explosivity Index. The thought experiment indicates that the Carbon Crater’s scale is comparable with large historical biospheric events. These results likely confer few direct implications for the study of the paleoclimate in climate modeling but might change conceptual understandings of atmospheric human waste. Additional empirical research is required to understand the potential impact of the Carbon Crater on conceptual change.

Catalytic Transformation of Biomass into Sustainable Carbocycles: Recent Advances, Prospects, and Challenges.

Organic compounds bearing one or more carbocycles in their molecular structure have a discernible presence in all major classes of organic products of industrial significance. However, sourcing carbocyclic compounds from exhaustible, anthropogenic carbon (e.g., petroleum) raises serious concerns about sustainability in the chemical industries. This review discusses recent advances in the renewable synthesis of carbocyclic compounds from biomass components following catalytic pathways. The mechanistic insights, process optimizations, green metrics, and alternative synthetic strategies of carbocyclic compounds have been detailed. Moreover, the renewable syntheses of carbocycles have been assessed against their existing synthetic routes from petroleum for better perspectives on their sustainability and technological preparedness. This work will assist the researchers in acquiring updated information on the sustainable synthesis of carbocyclic compounds from various biomass components, comprehending the research gaps, and developing superior synthetic processes for their commercial production.

Nanoscale Understanding on CO2 Diffusion and Adsorption in Clay Matrix Nanopores: Implications for Carbon Geosequestration.

Carbon capture and storage (CCS) in subsurface reservoirs represents a highly promising and viable strategy for mitigating global carbon emissions. In the context of CCS implementation, it is particularly crucial to understand the complex molecular diffusive and adsorptive behaviors of anthropogenic carbon dioxide (CO2) in the subsurface at the nanoscale. Yet, conventional molecular models typically represent only single-slit pores and overlook the complexity of interconnected nanopores. In this work, finite kaolinite lamellar assemblages with abundant nanopores (r < 2 nm) were used. Molecular dynamics simulations were performed to quantify the spatial distribution correlations, adsorption preference, diffusivity, and residence time of the CO2 molecules in kaolinite nanopores. The movement of the CO2 molecules primarily occurs in the central and proximity regions of the siloxane surfaces, progressing from larger to smaller nanopores. CO2 prefers smaller nanopores over larger ones. The diffusion coefficients increase, while residence times decrease, with the pore size increasing, differing from typical slit-pore models due to the pore shape and interconnectivity. The perspectives in this study, which would be challenging in conventional slit-pore models, will facilitate our comprehension of the CO2 molecular behaviors in the complex subsurface clay sediments for developing quantitative estimation techniques throughout the CCS project durations.

Estimation of carbon emissions in various clustered regions of China based on OCO-2 satellite XCO2 data and random forest modelling

Atmospheric carbon dioxide (CO2) stands as one of the most important greenhouse gasses, with steadily increasing concentrations attributable to human activities. In the pursuit of reaching peak carbon and carbon neutrality goals, it is essential to quantify carbon emissions and evaluate carbon reduction strategies. To establish a high-precision observation with full time series and spatial coverage, a spatio-temporal interpolation method was developed to obtain XCO2 data over mainland China at a resolution of 0.5° × 0.5° for the years 2015–2021. An east-west gradient, higher levels in the east and lower levels in the west, was observed, exhibiting a seasonal pattern of elevation in spring and reduction in summer. Subsequently, the research area is classified into seven clusters based on time-series XCO2 anomalies (ΔXCO2) and ODIAC (Open Source Data Inventory of Anthropogenic Carbon Dioxide) carbon emission data. This classification aims to emphasize the differentiation of spatial heterogeneity in carbon emissions and the results highlight that regions with high ΔXCO2 reflect higher carbon emission. Finally, the carbon emissions of each cluster were estimated by using a random forest model individually yielding an R2 of approximately 0.6. For assessing the variables influencing carbon emission predictions, the importance of each variable was calculated. Specifically, NightTime Lighting data (NTL), representing human production activities, emerged as a crucial variable influencing carbon emission predictions in most clusters. In comparison, Gross Primary Productivity (GPP) is considered a more critical variable in Southwest China (SWC), primarily owing to the intricate vegetation carbon sink system in this region. Temperature (T) emerges as a key variable influencing the estimation of carbon emissions in certain developed cities in Eastern China (EC), driven by the urban heat island effect which amplifies energy consumption, modifies land use, and impacts urban systems, influencing the spatial patterns of carbon emissions. Carbon emissions in different characteristic regions was quantified by establishing machine learning models with remote sensing data, which can provide new insights and support for refined carbon monitoring and management strategy.

Deforestation—a call for consistent carbon accounting

Abstract Carbon accounting conventions treat emissions differently depending on their source. Fossil fuel carbon emissions are assessed as gross, whereas anthropogenic land carbon emissions are assessed as net. Despite calls for consistent gross accounting, accounting guidelines remain unchanged. Here we consolidate arguments for consistent accounting and explore implications for national inventories, sector contributions, carbon markets and forest protection programs. We find consistent gross accounting useful for programs supporting forest preservation, deforestation reduction and reforestation, as well as consistency with carbon markets.

Ocean Alkalinity Enhancement in Deep Water Formation Regions Under Low and High Emission Pathways

AbstractOcean Alkalinity Enhancement (OAE) is an ocean‐based Carbon Dioxide Removal (CDR) method to mitigate climate change. Studies to characterize regional differences in OAE efficiencies and biogeochemical effects are still sparse. As subduction regions play a pivotal role for anthropogenic carbon uptake and centennial storage, we here evaluate OAE efficiencies in the subduction regions of the Southern Ocean, the Northwest Atlantic, and the Norwegian‐Barents Sea region. Using the ocean biogeochemistry model FESOM2.1‐REcoM3, we simulate continuous OAE globally and in the subduction regions under high (SSP3‐7.0) and low (SSP1‐2.6) emission scenarios. The OAE efficiency calculated by two different metrics is higher (by 8%–30%) for SSP3‐7.0 than for SSP1‐2.6 due to a lower buffer factor in a high‐ world. All subduction regions show a CDR potential (0.23–0.31; PgC uptake per Pg alkaline material) consistent with global OAE for both emission scenarios. Calculating the efficiency as the ratio of excess dissolved inorganic carbon (DIC) to excess alkalinity shows that the Southern Ocean and the Northwest Atlantic are as efficient as the global ocean (0.79–0.85), while the Norwegian‐Barents Sea region has a lower efficiency (0.65–0.75). The subduction regions store a fraction of excess carbon below 1 km that is 1.9 times higher than the global ocean. The excess surface alkalinity and thus uptake and storage follow the mixed‐layer depth seasonality, with the majority of the excess flux occurring in summer at shallow mixed layer depths. This study therefore highlights that subduction regions can be efficient for OAE if optimal deployment strategies are developed.

Sustainable Production of Biofuels from Biomass Feedstocks Using Modified Montmorillonite Catalysts.

The rampant exploitation of fossil fuels has led to the significant energy scarcity and environmental disruption, affecting the sound momentum of development and progress of human civilization. To build a closed-loop anthropogenic carbon cycle, development of biofuels employing sustainable biomass feedstocks stands at the forefront of advancing carbon neutrality, yet its widespread adoption is mainly hampered by the high production costs. Montmorillonite, however, has garnered considerable attention serving as an efficient heterogeneous catalyst of ideal economic feasibility for biofuel production, primarily due to its affordability, accessibility, stability, and excellent plasticity. Up to now, nevertheless, it has merely received finite concerns and interests in production of various biofuels using montmorillonite-based catalysts. There is no timely and comprehensive review that addresses this latest relevant progress. This review fills the gap by providing a systematically review and summary in controllable synthesis, performance enhancement, and applications related to different kinds of biofuels including biodiesel, biohydrogenated diesel, levulinate, γ-valerolactone, 5-ethoxymethylfurfural, gaseous biofuels (CO, H2), and cycloalkane, by using montmorillonite catalysts and its modified forms. Particularly, this review critically depicts the design strategies for montmorillonite, illustrates the relevant reaction mechanisms, and assesses their economic viability, realizing sustainable biofuels production via efficient biomass valorization.

Cross-frontal variability of phytoplankton productivity in the Indian sector of the Southern Ocean during austral summer of 2010–2018

Oceanic phytoplankton productivity, which regulates atmospheric CO2, is crucial for unraveling the complexities of the global carbon cycle. Despite its substantial contribution to the global carbon budget and its critical role in anthropogenic carbon sink, the Southern Ocean (SO) remains under-sampled due to logistical challenges. The present study attempts to elucidate the variability of water column primary production (PP) in the Indian Sector of the Southern Ocean (ISSO) by examining associated physicochemical parameters and physiological conditions of phytoplankton that drive this variability. The study revealed the nutrient limitation in the region north of the Subantarctic Front (SAF) and light limitation coupled with intense zooplankton grazing in the region south of the SAF. Coastal waters exhibit higher PP, characterized by the prevalence of large phytoplankton. The SAF displayed maximum productivity among the fronts, while the Polar Front 2 (PF-2) recorded the lowest. The water column PP varies from 27.01 to 960.69 mg C m−2 d−1 in the frontal region, while the coastal waters recorded productivity up to 1083.56 mg C m−2 d−1. Phytoplankton in the frontal regions indicated a stable surface abundance, except north of the Subtropical Front (STF), where the oligotrophic condition fosters the growth of picoplankton, subjected to high grazing by microzooplankton. Conversely, in the colder coastal waters, the phytoplankton experienced physiological acclimation. Model-based estimates of PP highlighted the efficacy of the Carbon-based Production Model (CbPM) in estimating net PP (NPP) in these polar waters, surpassing the Vertically Generalized Production Model (VGPM) and Eppley-VGPM. Notably, all model-based PP estimates significantly improved with in situ chlorophyll as input instead of satellite-retrieved chlorophyll. While the models performed well in the coastal water, their performance was suboptimal in the frontal region. This study advances our understanding of the intricate dynamics of phytoplankton productivity in the SO, offering valuable insights for future research endeavors.

Pacific Ocean-originated anthropogenic carbon and its long-term variations in the South China Sea.

Coastal oceans, traditionally seen as a conduit for transporting atmospheric carbon dioxide (CO2)-derived anthropogenic carbon (CANT) to open oceans, exhibit complex carbon exchanges at their interface. South China Sea (SCS) exemplifies this complexity, where interactions with the Pacific, particularly through Kuroshio intrusion, challenge the understanding of CANT source and variability in a coastal ocean. Contrary to prevailing paradigm expectations, our high-resolution, long-term data reveal that CANT in the SCS primarily originates from Pacific water injection across the Luzon Strait rather than atmospheric CO2 invasion. Over the past two decades, the SCS has experienced increasing CANT levels, with notable interannual fluctuations driven by El Niño and La Niña events influencing Kuroshio intrusion, generating anomalously high and low CANT inventories, respectively. This highlights an overlooked CANT transport pathway from open to coastal oceans, responsible for cumulative ocean acidification that has already affected coral reefs enriched in the SCS located west of the Coral Triangle.

Modelling of Joule-Thomson cooling effect using a modified shift-DeepONet method for predicting hydrate onset during CO2 sequestration

Carbon Storage in underground depleted oil and gas reservoirs play a key role in reducing anthropogenic Carbon Dioxide (CO2) emissions around the world. Injection of CO2 at high pressure into a low pressure depleted gas formations containing methane (CH4) leads to Joule-Thompson (J-T) cooling, possibly resulting in injection blocking precipitation of CO2 or CH4 hydrates. Here, we present a deep neural operator-based approach to model the J-T effects during CO2 injection in depleted reservoirs to demonstrate the effectiveness of Deep Operator Networks (DeepONets) in modelling piece-wise functions with sharp changes in gradient for cases of varying permeabilities. We propose a modified version of the shift-DeepONet model using non-linear constructors in the neural network architecture to accurately model temperature and pressure profiles in space and time. The modified shift-DeepONet model achieves a higher accuracy in modelling temperature for permeability in the range of 1.01mD to 101mD with three to up to ten times improvement in reducing Relative L2 (RL2) norm and with a testing RL2 norm of 3.8 × 10−4 compared to 2.97 × 10−3 for the Vanilla DeepONet. Using the temperature and pressure profiles, estimates are made for hydrate onset in space and time. The proposed modified shift-DeepONet method achieves high accuracy in hydrate classification with precision values > 0.99, recall values > 0.86 and F1 scores >0.92 in classification of CO2 or CH4 hydrate onset during CO2 injection into depleted gas reservoirs.

Changing circulations challenge the sustainability of cold water mass and associated ecosystem under climate change

Bottom cold water mass provides abundant nutrients and cool water in summer, playing a pivotal role in the productivity of marine ecosystem and sustainable aquaculture development. Located in the most densely populated region, the Yellow Sea cold water mass (YSCWM) is a unique one influencing hundreds of millions of people living in the rim of the Yellow Sea. As anthropogenic carbon emissions continue, how the YSCWM will be altered by climate change becomes a pressing issue, but remains elusive. Using an unprecedented set of climate models with high resolution and biogeochemical components, we find that the volume of the YSCWM will shrink by 48% to 2040–2050, along with the bottom temperature warming of 0.4 ± 0.1 °C dec−1 and the dissolved oxygen concentration declining of 0.09 ± 0.04 mg (L dec)−1. The significant destruction of the YSCWM is driven by the strengthened Yellow Sea Warm Current (YSWC). The reduced land-sea thermal contrast is the cause of the circulation change, by weakening the East Asian winter monsoon. Due to the resultant profound habitat reduction for marine life, predicting the change of the YSCWM will have far-reaching influences on the future policy-making for sustainable development of offshore aquaculture.

Re-identifying farmland carbon neutrality gap under a new carbon counting and the framework of regional interactions in China

The farmland ecosystem, with its numerous material cycles and energy flows, is an important part of the carbon cycle in terrestrial ecosystems. Focusing on the carbon neutrality of farmland is meaningful for mitigating global warming and serving national low-carbon strategies. This study enriches the carbon accounting items of farmland and establishes a new research framework to check the carbon neutrality of farmland from the aspect of regional interactions and, subsequently, the inequality among China's provinces. The results revealed that there is still a great gap in the capability of China's farmland to reach carbon neutrality, with a gap value of up to 10,503 × 104 t C. All of the provinces presented net carbon emissions, and the per unit area carbon neutrality gaps showed spatial regularity decreasing from the coastal regions to the inland areas. Anthropogenic carbon emissions on farmland played a dominant role compared with soil organic carbon. Five provinces had reduced interior-regional carbon emissions through grain trade, and the amounts were especially high for developed regions, such as Guangdong, Zhejiang, Beijing, Shanghai and Jiangsu. Sixteen provinces gained external carbon emissions through trade; these were the less developed regions located mainly in the north, such as Inner Mongolia, Hebei, Jilin, Heilongjiang and Xinjiang. Under regional inequality, 15 provinces added to the net amount of the carbon emissions generated in external regions, with China's megacities adding the highest percentage, especially Beijing, with 389.95 % compared with its original emissions. Inequality showed that most provinces had a moderate status. Sichuan and Hunan experienced weak advantages, and six provinces had disadvantages. Therefore, constructing compensation and trade-based rights and responsibilities traceability mechanisms is important.

Research and analysis of urban-rural residential carbon emissions in China

Residential carbon emissions are an important component of anthropogenic carbon emissions. a significant increase in residential carbon emissions has become a reality under the global urbanization process. In this context, this paper built a feature combination value model based on NPP-VIIRS nighttime light remote sensing data, and divided urban-rural areas through breakpoint analysis method and reference comparison method. Then, explored the characteristics and differences of residential carbon emissions and per capita residential carbon emissions in nine different levels of cities in 2019 from the perspective of urban-rural areas. The results indicate that the residential carbon emissions and per capita residential carbon emissions shows the spatial distribution characteristics of first tier cities>second tier cities>third tier cities. Among them, the residential carbon emissions in Beijing, Guangzhou, Nanjing, Taiyuan show a distribution pattern of urban>urban-rural fringe>rural. The residential carbon emissions in Shijiazhuang, Wuxi, Xiangyang, Zunyi, Huai’an show a distribution pattern of rural>urban-rural fringe>urban. The per capita residential carbon emissions of urban areas are relatively low, while the per capita residential carbon emissions of rural areas are relatively high, show a distribution pattern of rural>urban-rural fringe >urban. The results can help the Chinese government balance the needs of urban-rural development in different levels of cities, so as to formulate targeted carbon emission reduction policies and achieve low-carbon goals.

Examining the Importance of Hydrogen Bonding and Proton Transfer in Iron Porphyrin-Mediated Carbon Dioxide Upconversion.

ConspectusThe title should give a sense of the "big picture" of this Account, but what is it really about? An unexpected change in research direction? A series of courageous and creative students? A team taking on challenging problems in chemistry? The answer is a definite "yes" to all of the above. More specifically, the problem in which we are interested is the upconversion or valorization of carbon dioxide. This problem has captured the attention of a great many chemists in earnest following the gas crisis of the 1970s and more recently galvanized due to climate concerns arising from the ongoing release of anthropogenic carbon. Addressing the problem of atmospheric carbon accumulation requires effort in two very broad areas: capture and conversion. Storage is an alternative to conversion, but this eliminates the opportunity to use what might be otherwise a waste product. Our group has investigated a series of modified versions of iron(III)-5,10,15,20-tetraphenylporphyrin (FeTPP) that can convert CO2 to carbon monoxide, which is a versatile and useful precursor for other syntheses. Following pioneering work from Savéant and his colleagues in the 1990s and thereafter, we started with a simple question: how many pendent ancillary groups that can donate H-bonds or protons are needed to support efficient CO2-to-CO conversion? Using a molecule with only one 2-hydroxylphenyl group, we demonstrated that the single prepositioned -OH group gave rise to efficient turnover, but only when experiments were carried out in a weakly H-bond-accepting solvent system. In other words, the ability of a solvent to accept H-bonds can impede CO2 reduction. We followed up with a deeper investigation of the influence of H-bonding interactions with external acids in FeTPP-mediated CO2 reduction. Savéant's framework mechanism appears to be independent of solvent, and rate differences can be approximated by considering H-bonding equilibria. Following that work, we sought to better understand the minimum catalyst design requirements with respect to internal H-bond/proton donors. To that end, we produced all possible isomers of tetraarylpoprhyrins with 2,6-dihydroxyphenyl + phenyl groups. All else being equal, the complexes with a formally trans orientation of the 2,6-dihydroxyphenyl groups performed the best. Most recently, we surveyed the roles of internal and external Brønsted acids with different pKa values. Surprisingly, the best-performing catalysts have more weakly acidic internal groups. Overall, our work has demonstrated that CO2 reduction mediated by porphyrin catalysts can be improved by considering solvent H-bonding, the orientation of internal H-bonding groups, and the balance of the pKa values of internal and external acids. The future for molecular electrocatalysts is promising as more ideas emerge about how to design molecules and conditions for CO2 reduction.