Achieving satisfactory multi-carbon (C2+) products selectivity and current density under acidic condition is a key issue for practical application of electrochemical CO2 reduction reaction (CO2RR), ...but is challenging. Herein, we demonstrate that combining microenvironment modulation by porous channel structure and intrinsic catalytic activity enhancement via doping effect could promote efficient CO2RR toward C2+ products in acidic electrolyte (pH ≤ 1). The La-doped Cu hollow sphere with channels exhibits a C2+ products Faradaic efficiency (FE) of 86.2% with a partial current density of −775.8 mA cm−2. CO2 single-pass conversion efficiency for C2+ products can reach 52.8% at −900 mA cm−2. Moreover, the catalyst still maintains a high C2+ FE of 81.3% at −1 A cm−2. The channel structure plays a crucial role in accumulating K+ and OH- species near the catalyst surface and within the channels, which effectively suppresses the undesired hydrogen evolution and promotes C–C coupling. Additionally, the La doping enhances the generation of *CO intermediate, and also facilitates C2+ products formation.Efficient electroreduction of CO2 to multi-carbon products under strong acidic condition is highly challenging. Here, the authors demonstrate that combining microenvironment modulation and La doping effect could promote multicarbon products generation in acidic electrolyte.
Essential oils (
EO
s), as unique natural products, are promising resources for the discovery of green agrochemicals. The main ingredient geraniol of citronella oil was found to exhibit substantial ...antifungal activities in this study. Therefore, a series of novel geranyl aromatic sulfonamide compounds were synthesized and found to display considerable antifungal activities. Two geranyl thiofuran-sulfonamide compounds
4c-1
(median effective concentration (EC
50
) against
Rhizoctonia solani
: 24.97 mg/L and EC
50
against
Sclerotinia sclerotiorum
: 27.26 mg/L),
4c-2
(EC
50
against
S. sclerotiorum
: 18.53 mg/L) and one geranyl pyridine-sulfonamide compound
4d-2
(EC
50
against
R. solani
: 29.31 mg/L and EC
50
against
S. sclerotiorum
: 29.98 mg/L) were screened as “star molecules” due to their excellent antifungal activities. The preliminary structure-activity relationship (SAR) study revealed that the introduction of various aromatic heterocycles maybe an efficient protocol to improve the fungicidal activities of geranyl aromatic sulfonamide compounds. The molecular mechanisms of the geranyl aromatic sulfonamide compounds were clarified by performing molecular docking and molecular dynamics (MD) simulations. Three “star molecules” of these geranyl aromatic sulfonamide compounds were found to bind to Complex III through several hydrogen bonds and π-interactions with crucial residues TRP17, GLY20 etc. Their binding free energies were calculated to be strong ranging from −50.60 to −39.44 kcal/mol by MM/GBSA method, which suggested the geranyl aromatic sulfonamide compounds were potential Complex III inhibitors. The main component originating from the natural plant
EO
s ought to be studied in the future to discover novel pathogenic fungicidal candidates.
Graphical abstract
Efficient and sustainable amino acid synthesis is essential for industrial applications. Electrocatalytic reductive amination has emerged as a promising method, but challenges such as undesired side ...reactions and low efficiency persist. Herein, we demonstrated a lignin-derived catalyst for alanine synthesis. Carbon nanosheets (CNSs) were synthesized from lignin via a template-assisted method and doped with nitrogen and sulfur to boost reductive amination and suppress side reactions. The resulting N,S-co-doped carbon nanosheets (NS-CNSs) exhibited outstanding electrochemical performance. It achieved a maximum alanine Faradaic efficiency of 79.5%, and a yield exceeding 1,199 μmol h−1 cm−2 on NS-CNS, with a selectivity above 99.9%. NS-CNS showed excellent durability during long-term electrolysis. Kinetic studies including control experiments and theoretical calculations provided further insights into the reaction pathway. Moreover, NS-CNS catalysts demonstrated potential in upgrading real-world polylactic acid plastic waste, yielding value-added alanine with a selectivity over 75%.
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•Lignin NS-CNS catalyst enables 79.5% efficient electrocatalytic alanine synthesis•N,S-co-doping boosts amination and suppresses side reactions in alanine synthesis•Durable NS-CNS ensures lasting amino acid production performance•NS-CNS upgrades polylactic acid waste to value-added alanine
Electrochemical materials science; Nanoelectrochemistry; Applied chemistry
Many pundits and media believe that China under Mr. Xi Jinping is politically and economically illiberal with concentration of political power to Xi himself and the expansion of state capitalism. ...This article believes that China is still in transition and the Daobi (倒逼) mechanism, namely, a planned strategy of introducing foreign competition and international rules to advance domestic reform, takes effect. The EU-China Comprehensive Agreement on Investment (CAI) is a milestone that could possibly contribute to structural economic and even political changes in China. This article centres on the Daobi mechanism and explains how the synergies among CAI, domestic socioeconomic changes and Chinese leaders’ self-consciousness may set the agenda of China’s domestic reform.
CO2 electroreduction is of great significance to reduce CO2 emissions and complete the carbon cycle. However, the unavoidable carbonate formation and low CO2 utilization efficiency in neutral or ...alkaline electrolytes hinder its application at commercial scale. The development of CO2 reduction under acidic conditions provides a promising strategy, but the inhibition of the hydrogen evolution reaction is difficult. Herein, the first work to design a Ni–Cu dual atom catalyst supported on hollow nitrogen‐doped carbon is reported for pH‐universal CO2 electroreduction to CO. The catalyst shows a high CO Faradaic efficiency of ≈99% in acidic, neutral, and alkaline electrolytes, and the partial current densities of CO reach 190 ± 11, 225 ± 10, and 489 ± 14 mA cm−2, respectively. In particular, the CO2 utilization efficiency under acidic conditions reaches 64.3%, which is twice as high as that of alkaline conditions. Detailed study indicates the existence of electronic interaction between Ni and Cu atoms. The Cu atoms push the Ni d‐band center further toward the Fermi level, thereby accelerating the formation of *COOH. In addition, operando characterizations and density functional theory calculation are used to elucidate the possible reaction mechanism of CO2 to CO under acidic and alkaline electrolytes.
Compared with alkaline and neutral electrolytes, using an acidic electrolyte for the carbon dioxide reduction reaction (CO2RR) can significantly improve the carbon utilization efficiency. Herein, a Ni–Cu dual‐atom electrocatalyst is developed for pH‐universal CO2 electroreduction, which shows superior catalytic performance due to the electronic interaction between the Ni and the Cu. In particular, the carbon utilization efficiency increases from 33.0% to 64.3%.
Abstract
The renewable‐energy‐powered electroreduction of nitrate (NO
3
−
) to ammonia (NH
3
) has garnered significant interest as an eco‐friendly and promising substitute for the Haber–Bosch ...process. However, the sluggish kinetics hinders its application at a large scale. Herein, we first calculated the N‐containing species (*NO
3
and *NO
2
) binding energy and the free energy of the hydrogen evolution reaction over Cu with different metal dopants, and it was shown that Zn was a promising candidate. Based on the theoretical study, we designed and synthesized Zn‐doped Cu nanosheets, and the as‐prepared catalysts demonstrated excellent performance in NO
3
−
‐to‐NH
3
. The maximum Faradaic efficiency (FE) of NH
3
could reach 98.4 % with an outstanding yield rate of 5.8 mol g
−1
h
−1
, which is among the best results up to date. The catalyst also had excellent cycling stability. Meanwhile, it also presented a FE exceeding 90 % across a wide potential range and NO
3
−
concentration range. Detailed experimental and theoretical studies revealed that the Zn doping could modulate intermediates adsorption strength, enhance NO
2
−
conversion, change the *NO adsorption configuration to a bridge adsorption, and decrease the energy barrier, leading to the excellent catalytic performance for NO
3
−
‐to‐NH
3
.
Utilizing CO
2
as a carbon feedstock for producing fuels and useful chemicals is attractive due to the advantages of being abundant, nontoxic, and economical. Electrochemical CO
2
reduction (CO
2
RR) ...provides an avenue to close the anthropogenic carbon cycle. However, the reaction process of multi-electronic products of CO
2
RR is quite complex. It is hard to yield a target product with high selectivity, high current density, low overpotential, and good stability simultaneously. In recent years,
in situ/operando
characterization techniques have played important roles in the catalysis field
via
establishing the structure—reactivity/selectivity relationships of catalysts and thereby obtaining information about mechanisms. As a result, it is necessary to apply
in situ/operando
characterization technologies to clarify the reaction pathway of CO
2
RR. In this mini-review, we discuss recent progress on the
in situ/operando
characterizations for electrochemical CO
2
RR, including microscopies, infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption fine spectroscopy. Moreover, the capabilities of these
in situ/operando
characterizations and the remaining challenges are also discussed.
Realizing industrial‐scale production of HCOOH from the CO2 reduction reaction (CO2RR) is very important, but the current density as well as the electrochemical potential window are still limited to ...date. Herein, we achieved this by integration of chemical adsorption and electrocatalytic capabilities for the CO2RR via anchoring In nanoparticles (NPs) on biomass‐derived substrates to create In/X−C (X=N, P, B) bifunctional active centers. The In NPs/chitosan‐derived N‐doped defective graphene (In/N‐dG) catalyst had outstanding performance for the CO2RR with a nearly 100 % Faradaic efficiency (FE) of HCOOH across a wide potential window. Particularly, at 1.2 A ⋅ cm−2 high current density, the FE of HCOOH was as high as 96.0 %, and the reduction potential was as low as −1.17 V vs RHE. When using a membrane electrode assembly (MEA), a pure HCOOH solution could be obtained at the cathode without further separation and purification. The FE of HCOOH was still up to 93.3 % at 0.52 A ⋅ cm−2, and the HCOOH production rate could reach 9.051 mmol ⋅ h−1 ⋅ cm−2. Our results suggested that the defects and multilayer structure in In/N‐dG could not only enhance CO2 chemical adsorption capability, but also trigger the formation of an electron‐rich catalytic environment around In sites to promote the generation of HCOOH.
Indium nanoparticles on chitosan‐derived N‐doped defective graphene (In/N‐dG) create bifunctional active centers that integrate chemical adsorption and electrocatalytic capabilities for CO2 electrolysis. The electrocatalyst demonstrated outstanding performance for the CO2 reduction reaction with a nearly 100 % Faradaic efficiency toward HCOOH across a wide potential window and with high current density.
As an atmosphere conducive for scientific inquiry and research improves in China, many Chinese scholars are optimistic about the future development of International Relations (IR) studies. A younger ...generation of IR scholars has started to pay more attention to IR theory and begun to research issues like national sovereignty and China's national interests. This paper reviews the development of IR theory in China and the basic arguments among Chinese scholars on theory building, especially concerning the attempt to build an IR theory with 'Chinese characteristics'. It examines the reasons for the continuing challenges, amid progress, of IR theory in China and looks into the prospects in the near future.
Developing electrocatalytic reactions with high‐efficiency can make important contributions to carbon neutrality. However, poor long‐term stability of catalysts is a bottleneck for its practical ...application. Herein, an “in situ periodic regeneration of catalyst (PR‐C)” strategy is proposed to give long‐term high efficiency of CO2 electroreduction to generate C2+ products over Cu catalyst by applying a positive potential pulse for a short time periodically in the halide‐containing electrolyte. The high Faradaic efficiency (81.2 %) and current density (22.6 mA cm−2) could be maintained completely at least 36 h, while the activity and selectivity decreased continuously without using the PR‐C method. Control experiments and operando characterization demonstrated that the surface structure and oxidation state of Cu could be recovered periodically by the PR‐C method, which was beneficial for CO2 activation and C−C coupling.
An “in situ periodic regeneration of catalyst (PR‐C)” strategy is proposed to maintain the high efficiency of CO2 electroreduction towards C2+ products over a copper catalyst. A positive potential pulse is applied periodically for a short time in the halide‐containing electrolyte. As a result the surface structure and oxidation state of the Cu could be recovered periodically by the PR‐C method.
