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Electrochemical reduction of CO2 is an important way to achieve carbon neutrality, and much effort has been devoted to the design of active sites. Apart from elevating the intrinsic activity, expanding the functionality of active sites may also boost catalytic performance. Here we designed "negatively charged Ag (nc‐Ag)" active sites featuring both the intrinsic activity and the capability of regulating microenvironment, through modifying Ag nanoparticles with atomically dispersed Sn species. Different from conventional active sites (which only mediate the surface processes by bonding with the intermediates), the nc‐Ag sites could also manipulate environmental species. Therefore, the sites could not only activate CO2, but also regulate interfacial H2O and CO2, as confirmed by operando spectroscopies. The catalyst delivers a high current density with a CO faradaic efficiency of 97 %. Our work here opens up new opportunities for the design of multifunctional electrocatalytic active sites. [ABSTRACT FROM AUTHOR]

Renewable-energy-powered electrochemical CO2 reduction (ECR) is a promising way of transforming CO2 to value-added products and achieving sustainable carbon recycling. By virtue of the extremely high exposure rate of active sites and excellent catalytic performance, atomic site catalysts (ASCs), including single-atomic site catalysts and diatomic site catalysts, have attracted considerable attention. In this feature article, we focus on the rational design strategies of ASCs developed in recent years for the ECR reaction. The influence of these strategies on the activity and selectivity of ASCs for ECR is further discussed in terms of electronic regulation, synergistic activation, microenvironmental regulation and tandem catalytic system construction. Finally, the challenges and future directions are indicated. We hope that this feature article will be helpful in the development of novel ASCs for ECR. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Nano‐catalysis plays a vital role in the industrially chemical transformations. The increasingly severe energy crisis and environmental issues spur scientists to exploit novel nano‐catalysts in diverse fields. It is essential to understand the fundamental physicochemical properties of nano‐catalysts to develop efficient systems, whose design can be subsequently precisely tuned at the atomic level. In this review, we summarize several key factors affecting the catalytic activity of nano‐catalysts, including structure, composition, size, and interface, providing guidance for the atomic level control of high‐efficient nano‐catalysts. Finally, we present a brief conclusion and some thoughts on nano‐catalysis. What is the most favorite and original chemistry developed in your research group? Nanomaterials for catalysis and renewable energy. How do you supervise your students? I always encourage my students to innovate, persist and enjoy their researches. What is the most important personality for scientific research? Strong interest. What are your hobbies? What's your favorite book(s)? Reading, travelling and gaming. My favorite books are novels that give me a variety of different experiences. How do you keep balance between research and family? I always try to make time to be with my family, however busy I am. [ABSTRACT FROM AUTHOR]

The development of highly active and stable bifunctional noble‐metal‐based electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is a crucial goal for clean and renewable energy, which still remains challenging. Herein, we report an efficient and stable catalyst comprising a Co single atom incorporated in an RuO2 sphere for HER and OER, in which the Co single atom in the RuO2 sphere was confirmed by XAS, AC‐STEM, and DFT. This tailoring strategy uses a Co single atom to modify the electronic structures of the surrounding Ru atoms and thereby remarkably elevates the electrocatalytic activities. The catalyst requires ultralow overpotentials, 45 mV for HER and 200 mV for OER, to deliver a current density of 10 mA cm−2. The theoretical calculations reveal that the energy barriers for HER and OER are lowered after incorporation of a cobalt single atom. [ABSTRACT FROM AUTHOR]

Large scale synthesis of high-efficiency bifunctional electrocatalyst based on cost-effective and earth-abundant transition metal for overall water splitting in the alkaline environment is indispensable for renewable energy conversion. In this regard, meticulous design of active sites and probing their catalytic mechanism on both cathode and anode with different reaction environment at molecular-scale are vitally necessary. Herein, a coordination environment inheriting strategy is presented for designing low-coordination Ni2+ octahedra (L-Ni-8) atomic interface at a high concentration (4.6 at.%). Advanced spectroscopic techniques and theoretical calculations reveal that the self-matching electron delocalization and localization state at L-Ni-8 atomic interface enable an ideal reaction environment at both cathode and anode. To improve the efficiency of using the self-modification reaction environment at L-Ni-8, all of the structural features, including high atom economy, mass transfer, and electron transfer, are integrated together from atomic-scale to macro-scale. At high current density of 500 mA/cm2, the samples synthesized at gram-scale can deliver low hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of 262 and 348 mV, respectively. [ABSTRACT FROM AUTHOR]

For electrocatalysts for the hydrogen evolution reaction (HER), encapsulating transition metal phosphides (TMPs) into nitrogen‐doped carbon materials has been known as an effective strategy to elevate the activity and stability. Yet still, it remains unclear how the TMPs work synergistically with the N‐doped support, and which N configuration (pyridinic N, pyrrolic N, or graphitic N) contributes predominantly to the synergy. Here we present a HER electrocatalyst (denoted as MoP@NCHSs) comprising MoP nanoparticles encapsulated in N‐doped carbon hollow spheres, which displays excellent activity and stability for HER in alkaline media. Results of experimental investigations and theoretical calculations indicate that the synergy between MoP and the pyridinic N can most effectively promote the HER in alkaline media. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of CO 2 is an important way to achieve carbon neutrality, and much effort has been devoted to the design of active sites. Apart from elevating the intrinsic activity, expanding the functionality of active sites may also boost catalytic performance. Here we designed "negatively charged Ag (nc-Ag)" active sites featuring both the intrinsic activity and the capability of regulating microenvironment, through modifying Ag nanoparticles with atomically dispersed Sn species. Different from conventional active sites (which only mediate the surface processes by bonding with the intermediates), the nc-Ag sites could also manipulate environmental species. Therefore, the sites could not only activate CO 2 , but also regulate interfacial H 2 O and CO 2 , as confirmed by operando spectroscopies. The catalyst delivers a high current density with a CO faradaic efficiency of 97 %. Our work here opens up new opportunities for the design of multifunctional electrocatalytic active sites., (© 2024 Wiley-VCH GmbH.)

Electrochemical CO 2 reduction reaction (CO 2 RR) provides a promising route to converting CO 2 into value-added chemicals and to neutralizing the greenhouse gas emission. For the industrial application of CO 2 RR, high-performance electrocatalysts featuring high activities and selectivities are essential. It has been demonstrated that customizing the catalyst surface/interface structures allows for high-precision control over the microenvironment for catalysis as well as the adsorption/desorption behaviors of key reaction intermediates in CO 2 RR, thereby elevating the activity, selectivity and stability of the electrocatalysts. In this paper, we review the progress in customizing the surface/interface structures for CO 2 RR electrocatalysts (including atomic-site catalysts, metal catalysts, and metal/oxide catalysts). From the perspectives of coordination engineering, atomic interface design, surface modification, and hetero-interface construction, we delineate the resulting specific alterations in surface/interface structures, and their effect on the CO 2 RR process. At the end of this review, we present a brief discussion and outlook on the current challenges and future directions for achieving high-efficiency CO 2 RR via surface/interface engineering., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Copper (Cu), a promising catalyst for electrochemical CO 2 reduction (CO 2 R) to multi-electron reduction products, suffers from an unavoidable and uncontrollable reconstruction process during the reaction, which not only may lead to catalyst deactivation but also brings great challenges to the exploration of the structure-performance relationship. Herein, we present an efficient strategy for stabilizing Cu with silica and synthesize reconstruction-resistant CuSiO x amorphous nanotube catalysts with abundant atomic Cu-O-Si interfacial sites. The strong interfacial interaction between Cu and silica makes the Cu-O-Si interfacial sites ultrastable in the CO 2 R reaction without any apparent reconstruction, thus exhibiting high CO 2 -to-CH 4 selectivity (72.5%) and stability (FE CH 4 remains above 60% after 12 h of test). A remarkable CO 2 -to-CH 4 conversion rate of 0.22 μmol cm -2 s -1 was also achieved in a flow cell device. This work provides a very promising route for the design of highly active and stable Cu-based CO 2 R catalysts.

Herein, we report the unusual broadband white-light emission as an intrinsic property from two cationic lead bromide frameworks. This is the first time that the metal halide materials adopting a purely inorganic positively-charged three-dimensional (3D) topology have been synthesized, thus affording highly distorted Pb II centers. The single-component white-light emitters achieve an external quantum efficiency of up to 5.6% and a correlated color temperature of 5727 K, producing typical white-light close to that of fluorescent light sources. Unlike the air/moisture-sensitive 3D organolead halide perovskites, our cationic materials are chemically "inert" over a wide range of pH as well as aqueous boiling condition. Importantly, these long-sought ultrastable lead halide materials exhibit undiminished photoluminescence upon continuous UV-irradiation for 30 days under atmospheric condition (∼60% relative humidity, 1 bar). Our mechanistic studies indicate the broadband emission have contributions from the self-trapped excited states through electron-vibrational coupling in the highly deformable and anharmonic lattice, as demonstrated by variable-temperature photoluminescence/absorption spectra as well as X-ray crystallography studies. The chemical robustness and structural tunability of the 3D cationic bromoplumbates open new paths for the rational design of hybrid bulk emitters with high photostability.