bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Hydrogen Atom Transfer Coupled Dye-Sensitized Photoelectrochemical Cell for Lignin Decomposition
Authors: Kang Hyeong Cheol , Kim Saerona , Yoo Kicheon , Leem Gyu , Lee Jae-Joon 
Published: November 2022

For the decomposition process of lignin, there have been several processes reported. However, low selectivity of oxidative cleavage is one of prime issues because of reaction under harsh condition such as high temperature and high pressure. To overcome these problems, especially, dye-sensitized photo-electrochemical cells (HAT-DSPEC), which used photocatalyst (RuC) and homogeneous catalysts incorporated system was suggested. it represents conversion efficiencies over 90% under 24 h light illumination (AM 1.5G). However, metal complex sensitizer has disadvantages like low stability, high cost and low absorption coefficient.
In this study, for highly stable HAT-DSPEC process, metal based sensitizer was replaced by organic dye(5-[4-(diphenylamino)phenyl]thiophene-2-cyanoacrylic acid, L1) which has high stability and molar absorption coefficient. For regenerating dye molecules and oxidating lignin model compounds(LMCs), bicyclic nitroxyl derivates, such as 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and 9-azabicyclo[3,3,1]nonan-3-one-9-oxyl (Keto-ABNO) was used. In HAT-ODSPEC (organic dye-sesitized photo-electrochemical cell), Keto-ABNO exhibits higher photo-electrocatalytic activity than TEMPO for the oxidation and decomposition of LMC. The superior activity of L1 sensitizer with Keto-ABNO mediator is especially noteworthy of Caryl-Cα bond cleavage and with keto-ABNO exhibits 100% conversion yield of for 24hrs at room temperature while 86% with TEMPO. This HAT-ODSPEC process provides a unique foundation to perform selective C−C bond cleavage for real lignin conversion technologies.
(Invited, Digital Presentation) Methane Conversion to High Value Chemicals By Photocatalysis
Authors: Tang Junwang 
Published: November 2022

As underlined in the COP26, methane as a greenhouse gas is nearly 80 time more potent than CO2 while its reserve is much more than the sum of coal, oil and natural gas. Thus methane conversion not only involves the environmental issue but also is related to high-value chemical production /clean energy supply, which has been attracting substantial interest over the last decades. However CH4 activation is energy intensive and kinetically very challenging so that methane activation is regarded as the “holy grail” in the catalytically chemical process. [1] Photocatalysis provides a cost efficient potential to activation of such small molecule under very mild conditions, while to achieve the potential is a huge challenge.[2]
Stimulated by our research outcomes on the charge dynamics in inorganic semiconductor photocatalysis, which reveal that the low reaction efficiency is due to both fast charge recombination and large bandgap of an inorganic semiconductor [3,4], together with the recent findings on atomic catalysis [5], we developed novel material strategies for photocatalytic methane conversion to methanol.
Highly dispersed atomic level iron species immobilised on a TiO2 photocatalyst show an excellent activity for methane conversion, resulting into ~97% selectivity towards alcohols operated under ambient conditions by a one-step chemical process [6]. Such photocatalyst is also very stable, promising an attractive industrial process of methane upgrade. The dominating function of the iron species has also been investigated in detail. Furthermore, we designed a flow system for relatively efficient methane to C2, achieving the benchmark results in this area.[7] In addition, C1 oxygenates can be produced with nearly 100% by photocatalytic methane conversion due to the synergy between Au and Cu cocatalysts loaded on ZnO.[8]

References
：

Li, X. Wang, C., Tang, J.
Nature Reviews Materials
, 2022, Doi: 1038/s41578-022-00422-3.

Wang Y., Suzuki H., Xie, J., Tomita, O., Martin, D. J., Higashi, M., Kong, D., Abe R. Tang, J.,
Chem. Rev., 2018, 118: 5201-5241.

Tang, J. Durrant J. R., Klug, R .,
J. Am. Chem. Soc

., 2008, 130(42) : 13885-13891.

Miao, T., Wang, C., Xiong, L., Li, X., Xie, X., Tang, J.,
ACS Catalysis
, 2021, 11, 8226-8238.

Wang, A. Li J., Zhang. T.,
Nat
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Rev. Chem

., 2018, 2; 65-81.

Xie, J., Jin, R. ,Li, A., Bi, Y., Sankar, G. , Ma , Tang, J.
Nature Catalysis

, 2018, 1: 889-896.

Li, X., Xie J.,Rao, H., Wang, , Tang, J.,
Angewandte Chemie International Edition

, 2020, 132: 19870-19875.

Luo, L., Gong, Z., Xu, Y., Ma, J., Liu, H., Xing, J., Tang, J.,
Journal of the American Chemical Society
, 2022, 144, 2, 740–750.
(Invited) Ultrafast Spectroscopy Measurements of Lead-Halide Hybrid Semiconductor Nanocrystals for Photocatalysis
Authors: Beard Matt C 
Published: November 2022

We are exploring the use of metal-halide perovskite semiconductor nanocrystals (PNCs) as efficient photocatalysis. Heterogeneous photocatalysis are less common than homogeneous but can provide unique avenues for inducing novel chemical transformations and can also be utilized for energy transductions, i.e., the energy in the photons can be captured in chemical bonds. Additional, earth abundant nanocrystal based photocatalyst are highly sought after as they can potentially eliminate expensive noble metal catalyst. A detailed understand of the underlying reaction mechanism could provide guidance in designing new systems that can activate a larger class of small molecules. Here, we discuss transient absorption spectroscopy to study a model C-C bond formation reaction, i.e., alkylation of aldehydes catalyzed by colloidal CsPbBr3 NCs. We find that both electrons and holes undergo ultrafast charge transfer from photoexcited PNCs. After charge transfer the charge separated state lives ~ 1 ns enabling radical mechanism to form C-C bonds.
I will also discuss the use of PNCs to host a transition metal Cu-site incorporated at the surface of the PNCs to induce a to induce a N-N heterocyclization reaction. The reaction starts from surface coordinated diamine substrates and requires to subsequent photo-oxidation events. We established a photocatalytic cycle where photo-excited holes are funneled to the coordinated substrates.
(Invited, Digital Presentation) Application of in Situ X-Ray Spectroscopy Techniques for Studying CO2 Reduction Reaction
Authors: Yano Junko , Li Xiang , Kaminsky Corey , Sokaras Dimosthenis , Crumlin Ethan J. 
Published: November 2022

Artificial photosynthesis capable of the CO2 reduction reaction (CO2RR), with solar energy as external excitation energy and water (H2O) as the electron and proton source, has been considered an attractive method to achieve a sustainable energy cycle, since it allows direct solar-to-chemical energy conversion. To design such systems, X-ray techniques play an important role for gaining the fundamental understanding needed to tailor its components and assemblies, by providing their chemical and structural information [1-3]. We have utilized surface-sensitive soft and hard X-ray techniques to investigate the interaction of metal catalytic surfaces with electrolytes and/or gases (H2O and/or CO2) under in situ/operando conditions. Among those, Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS) probes CO2 adsorption on catalyst surfaces, providing the information of the initial atomic level events for CO2 electroreduction on the metal catalysts. In situ X-ray absorption spectroscopy, on the other hand, can complement the study by providing metal catalytic surface sensitive information. We discuss in situ studies of the CO2 reduction reaction, with Cu and related oxides and alloys.
Reference
[1] Lee, S.H.; Lin, J.C.; Farmand, M.; Landers, A.T.; Feaster, J.T.; Avilés Acosta, J.E.; Beeman, J.W.; Ye, Y.; Yano, J.; Mehta, A.; Davis, R.C.; Jaramillo, T.F.; Hahn, C.; Drisdell, W.S., J. Am. Chem. Soc.
143, 588–592 (2020).
[2] Ye, Y.; Su, J.; Lee, K.-J.; Larson, D.; Valero-Vidal, C.; Blum, M.; Yano, J.; Crumlin, E.J., J. Phys. D: Appl. Phys.
54, 234002 (2021).
[3] Ye, Y.; Qian, J.; Yang, H.; Su, H.; Lee, K. -J.; Etxebarria, A.; Cheng, T.; Xiao, H.; Yano, J.; Goddard, W. A.; Crumlin, E. J., ACS Appl. Mater. Interfaces,
12, 25374–25382 (2020).
(Invited) Ultrafast Charge Recombination and Localisation in Transition Metal Oxides with Extended Visible Light Absorption
Authors: Sachs Michael , Harnett-Caulfield Liam , Pastor Ernest , Nelson Jenny , Walsh Aron , Durrant James 
Published: November 2022

The development of materials with high activity for photocatalytic water splitting is a central challenge for the production of renewable hydrogen using sunlight. Owing to advantages such as low cost, elemental abundance, and chemical stability, transition metal oxides (TMOs) are some of the most widely used materials for this purpose. The most efficient systems developed to date reach solar-to-hydrogen conversion efficiencies (STH) of around 1%1 and are based on wide bandgap TMOs such as SrTiO3.2 Because such wide bandgap materials often absorb UV light only, TMOs with extended visible light absorption are key to bridge the activity gap towards the target for commercial applications,3 often considered to be 10% STH.
While large research efforts have been devoted to TMOs with smaller bandgaps, efficiencies for such materials have typically remained relatively far from their theoretical limit. For example, Fe2O3 is one of the most studied TMOs in the field of solar fuel production, but it has so far reached only 1/3 of its theoretical maximum activity for water oxidation,4 raising the question of limitations of more fundamental nature.
In this talk, I will discuss the links between ultrafast charge recombination and polaron formation in TMOs – two of the main processes considered to impose efficiency limitations. Firstly, Fe2O3, Cr2O3, and Co3O4, which have absorption onsets of around 2.1 eV, 1.9 eV, and 1.6 eV, respectively, are studied using time-resolved optical spectroscopic techniques to probe their excited state dynamics on a timescale of femtoseconds to seconds following light absorption. I will demonstrate how common photophysical features and dynamics suggest a shared pathway for the recombination and localisation of photogenerated charges in these materials, but with different branching ratios. Secondly, a comparison to wide bandgap metal oxides reveals a different relative importance of these recombination and localisation pathways compared to TMOs with smaller bandgaps. Taken together, a more general photophysical model emerges, providing insights into the performance limiting factors in TMOs, including those with extended visible light absorption.
References:

Wang, Q. et al. Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%. Nat. Mater. 1–3 (2016).

Takata, T. et al. Photocatalytic water splitting with a quantum efficiency of almost unity. Nature
581, 411–414 (2020).

Chen, S., Takata, T. & Domen, K. Particulate photocatalysts for overall water splitting. Nat. Rev. Mater.
2, 17050 (2017).

Kim, J. Y. et al. Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting. Sci. Rep.
3, 2681 (2013).
Using Synchrotron Based x-Ray Analysis to Understand the Influence of Cations on CO2 Electrolysis Performance
Authors: Garg Sahil , Xu Qiucheng , Moss Asger Barkholt , Mirolo Marta , Drnec Jakub , Seger Brian 
Published: November 2022

Given that society will always need carbon based products such as plastics, nylons and organic solvents and probably high density fuels for aviation and shipping, this entails there is an urgent need to produce carbon based products sustainably. CO2 electrolysis to building-block chemicals such as CO, ethanol, and ethylene shows great promise, however there is still substantial development and understanding needed to operate at industrially relevant current densities (>100 mA/cm2) and maintaining stable performance for 1000s of hours.
This talk will focus on using in synchrotron based x-rays to analyze a zero-gap membrane electrode CO2 electrolysis device in operando. Not only does x-ray diffraction allow us to see changing oxidation state of our copper catalyst, but we can also see the Bragg peaks of any formation of salt precipitations in-situ, which is a substantial issue in these devices since they block mass transfer. Furthermore by analyzing background scattering, we can also visualize electrolyte variations within our cathodic gas diffusion layer. By having our in-operando device attached to both an in-line gas chromatograph and mass spectrometer we can relate product variations to variation in parameters visualized via the x-ray analysis and thus have a more comprehensive understanding of our devices. In this talk, we will discuss how variations in both anode electrolyte concentration and type (e.g. Li, Cs) have a substantial impact in both electrolyte penetration into the cathodic gas diffusion layer as well as how and where these salts may precipitate out and cause mass transfer issues.
Large-Scale Synthesis of Photocatalytic TiO2 Nanotube Layers
Authors: Sopha Hanna , Baudys Michal , Krysa Josef , Macak Jan M. 
Published: November 2022

Self-organized TiO2 nanotube layers have attracted considerable scientific and technological interest over the past 15 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of the 1D TiO2 nanotube layers is carried out by a conventional electrochemical anodization of valve Ti metal sheets in various electrolytes.
By now, the synthesis of TiO2 nanotube layers with different nanotube dimensions (diameter, length) and the application of these nanotube layers is well established on the laboratory scale. However, for real applications outside the laboratory scale, such as photocatalysis [3], TiO2 nanotube layers of much larger size are necessary. To date, just a few efforts were carried out to scale up the size of the nanotube layers to more than a few cm2 [3-7] due to the difficulty of controlling the parameters of the anodization process on a larger scale. The main challenge is the huge current received during the anodization of large substrates. This, in turn, leads to an increase in the electrolyte temperature that may result in dielectric breakdown of the growing nanotube layers.
In this presentation, the preparation of TiO2 nanotube layers on larger area titanium substrates (dozens of cm2) will be discussed, taking into account the control of the anodization parameters. The TiO2 nanotube layers with different thicknesses and nanotube diameters were employed for gas phase photocatalysis, following the ISO standards [3,8]. Experimental details and photocatalytic results will be presented and discussed.
References
[1] J.M. Macak, H. Tsuchiya, A. Ghicov, K. Yasuda, R. Hahn, S. Bauer, P. Schmuki, Curr. Opin. Solid State Mater., 11 (2007) 3.
[2] K. Lee, A. Mazare, P. Schmuki, Chem. Rev., 114 (2014) 9385.
[3] H. Sopha, M. Baudys, M. Krbal, R. Zazpe, J. Prikryl, J. Krysa, J.M. Macak, Electrochem. Commun., 97 (2018) 91.
[4] S. Franz, D. Perego, O. Marchese, M. Bestetti, J. Water Chem. Tech., 37 (2015) 108.
[5] H.-I. Kim, D. Kim, W. Kim, Y.-C. Ha, S.-J. Sim, S. Kim, W. Choi, Appl. Catal. A: Gen., 521 (2016) 174.
[6] J.P. Ghosh, G. Achari, C.H. Langford, Water Environ. Res., 88 (2016) 785.
[7] C. Xiang, L. Sun, Y. Wang, G. Wang, X. Zhao, S. Zhang, J. Phys. Chem. C 121 (2017) 15448.
[8] H.Sopha, M. Baudys, J. Krýsa, J. M. Macak, Applied Mater. Today, submitted.
(Invited) Electrochemical Valorization of Waste Activated Sludge to Chemicals
Authors: Botte Gerardine G. 
Published: November 2022

Population growth have led to producing more solid waste from wastewater treatment plants (WWTPs), increasing both energy and cost for treatment and disposal of waste-activated sludge (WAS). If not treated properly, WAS poses serious threats to human health and the environment. The annual production of WAS reached 2 billion tons in 2011 worldwide and it is expected that this number will grow to 9.5 billion tons per year by 2050 [1]. Conversion of solid waste to value added chemicals and fuels could address environmental concerns imposed by the growing of WAS.
To confront these challenges, Botte’s research group is working in the electrochemical valorization of WAS to chemicals [2]. In this talk, we will describe recent findings in the electrocatalysis of sludge using transition metals for the synthesis of ammonia and short-chain fatty acids production. Short-chain fatty acids (e.g., acetic acid, propionic acid, butyric acid, etc.) are the intermediate chemicals in anaerobic digestion. The global market demand for short-chain fatty acids in 2020 was 18,500 kt and it is expected to increase annually by 3% per year over the next three years [3].
[1] Lemar, M.; De Fontaine, A., Energy Data Management Manual for the Wastewater Treatment Sector. Technical Report ORNL/SPR-2018/14 2017, United States. https://doi.org/10.2172/1432164
[2] Jafari, M.; Botte, G. G., Electrochemical treatment of sewage sludge and pathogen inactivation. Journal of Applied Electrochemistry
2021,
51 (1), 119-130.
[3] Ramos-Suarez, M.; Zhang, Y.; Outram, V., Current perspectives on acidogenic fermentation to produce volatile fatty acids from waste. Reviews in Environmental Science and Bio/Technology
2021,
20 (2), 439-478.
(Digital Presentation) Highly Efficient and Selective CO2 Electroreduction to CO on Novel Metal-Nitrogen-Carbon (M-N-C) Catalyst
Authors: Delafontaine Laurent , Cosenza Alessio , Murphy Eamonn , Guo Shengyuan , Liu Yuanchao , Chen Jiazhe "Loki" , Atanassov Plamen 
Published: November 2022

The electrocatalytic reduction of CO2 (CO2RR) to CO is an important component of emerging Carbon Capture and Utilization (CCU) technologies. This process often relies on expensive and rare metals such as silver and gold-based materials for high selectivity and conversion rate to CO1,2. It is desired to move away from these metals towards earth-abundant solid materials (e.g., carbon-based) which may serve as heterogeneous electrocatalysts for CO2RR. Herein, a series of novel carbon-based materials with exceptional selectivity/activity for the targeted production of CO is presented. This new class of hybrid catalyst materials have high CO2RR activity which is comparable to the state of the art atomically dispersed Metal-N-C synthesized by the sacrificial support method (SSM). The advantage of this new class of catalysts is that the use of harsh solvents such as nitric acid and potassium hydroxide which are usually required to remove the silica precursor is completely avoided. Not only does this make the immediate process more environmentally friendly, but it also significantly shortens the catalyst synthesis time which increases its industrial viability. The structure and activity of a series of catalysts with different metallic dopants (Fe, Co, Ni, Mn) are investigated. Using this new synthesis technique, a faradaic efficiency for CO formation (FEco) of 96.5 % at -0.3 V vs. RHE is achieved. FEco remains greater than 75 % over the potential range studied from -0.3 V to -1.1 V vs. RHE. By comparison, Fe-N-C by SSM method reaches a maximum FEco of 94.4 % at -0.7 V vs. RHE and FEco remains greater than 85 % over the same potential range.

References

1. Varela, A. S., Ranjbar Sahraie, N., Steinberg, J., Ju, W., Oh, H.-S., & Strasser, P. (2015). Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons. In Angewandte Chemie International Edition.
2. Nguyen, D. L. T., Kim, Y., Hwang, Y. J., & Won, D. H. (2019). Progress in development of electrocatalyst for CO 2 conversion to selective CO production. In Carbon Energy.

Figure 1
(Invited) Proton‐Conducting Solid Oxide Electrolysis Cells for Hydrogen Production - Materials Design and Catalyst Surface Engineering
Authors: Liu Xingbo , Tian Hanchen , Li Wenyuan 
Published: November 2022

Solid oxide steam electrolysis cell, a promising electrical-chemical conversion device for the next generation efficient hydrogen production and energy storage, has been actively studied because of their high energy conversion efficiencies and prospective applications as electrochemical reactors. After decades of research on protonic ceramic materials, remarkable advances have been made in the protonic ceramic electrochemical cells (PCECs) air electrode and electrolyte. However, the existing air electrodes are far from satisfying the requirements of practical applications, a series of issues, including the lack of active and durable electrodes, greatly limit the commercialization. To date, the systematic development of triple conducting catalysts remains abstruse because of the challenges of characterizing protonic behavior. A quantitative properties assessment and prediction on protonic properties of perovskite are still not available.
Starting with a computational fluid dynamic modeling on the protonic ceramic electrochemical cells (PCECs) air electrode, we focused on the materials design of air electrode materials by employing model guidance, operating durability optimization by electrode structure engineering, as well as the air electrode surface tailoring to overcome the most rate-limiting step. Thus, the electrochemical performance and durability of PCEC care comprehensively improved. The fabrication methods, characterization techniques with electrochemical performance are presented. Further work plans and implications are proposed regarding optimizing the structure of materials, preparation technology, and better understanding the role of these triple conductors. This research is expected to provide an in-depth understanding and offer avenues in the rational design of PCEC with long operational life and high energy/power density in the near future.
Interconnections between Solar-Driven Ammonia Production and the Water and Distribution Infrastructures at a Global Scale
Authors: Fernandez Carlos Arturo , Hatzell Marta 
Published: November 2022

Ammonia plays a crucial role in the modern agriculture industry, as synthetic nitrogenous fertilizers supply over half of the nitrogen input into croplands. However, ammonia production through the Haber-Bosch process contributes to 1.2% of the global anthropogenic CO2 emissions and 2% of the global energy consumption. Thus, momentum has been building to transition Ammonia production towards renewable and electrified approaches. There are inherent risks and opportunities associated with the adoption of new technologies, and electrifying ammonia production will likely result in a new decentralized market for green ammonia. This work opens the dialogue to consciously create a system that is resilient, sustainable, and globally available.
This talk presents a detailed geospatial study on solar-driven ammonia production. First, we identify the spatial distribution of solar-driven ammonia production while considering key economic and performance parameters such as capital cost and energy efficiency. We study how the ammonia production cost distribution changes with the implementation of different technologies (i.e., low-temperature electrochemical ammonia production, lithium-mediated electrochemical ammonia production, and the electrified Haber-Bosch process). Then, we identify key considerations and performance targets (Energy Efficiency, Capital Costs, and Distribution Costs) for solar-driven ammonia production to reach economic feasibility. Finally, we optimize solar-driven ammonia production and distribution networks to decrease production and transportation costs while increasing resiliency towards changes in distribution costs and water scarcity through multi-objective network optimization.

Figure 1