Recent advances of transition-metal metaphosphates for efficient electrocatalytic water splitting

Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.

Vacancy engineering induced reaction kinetics enhancement of cobalt metaphosphate for pH-universal hydrogen evolution

Developing efficient pH-universal hydrogen evolution reaction(HER)catalysts is critical in the field of water electrolysis,however,which is severely hampered by the sluggish kinetics in alkaline media.Herein,a ruthenium(Ru)incorporation induced vacancy engineering strategy is firstly proposed to precisely construct oxygen vacancy(V_(O))-riched cobalt-ruthenium metaphosphate(CRPO)for high-efficiency pH-universal HER.The V_(O) modifies the electronic structure,improves the superficial hydrophilic and gas spillover capacity,it also reduces the coordination number of Ru atoms and regulates the coordination environment.Theoretical calculations indicate that Ru tends to adsorb H_(2)O and H^(*),whereas V_(O) tends to adsorb OH^(-),which greatly promotes the H_(2)O adsorption and the dissociation of HO-H bond.Ultimately,CRPO-2 exhibits remarkable HER performance,the mass activity is about 18.34,21.73,and 38.07 times higher than that of Pt/C in acidic,neutral,and alkaline media,respectively,at the same time maintain excellent stability.Our findings may pave a new avenue for the rational design of electrocatalysts toward pH-universal water electrolysis.

Study on reactions of gaseous P_2O_5 with Ca_3(PO_4)_2 and SiO_2 during a rotary kiln process for phosphoric acid production

In a rotary kiln process for phosphoric acid production,the reaction between gaseous phosphorus pentoxide（P2O5）and phosphate ore and silica contained in feed balls（the so-called P2O5＂absorption＂）not only reduces phosphorous recovery but also generates a large amount of low melting-point side products.The products may give rise to formation of kiln ring,which interferes with kiln operation performance.In this study,the reactions of gaseous P2O5with solid calcium phosphate（Ca3（PO4）2）,silica（SiO2）and their mixture,respectively,were investigated via combined chemical analysis and various characterizations comprised of X-ray diffraction（XRD）,Fourier-transform infrared（FT-IR）spectroscopy,thermogravimetric analysis and differential scanning calorimeter（TG＆DSC）,and scanning electron microscopy and energy dispersive spectrometer（SEM＆EDS）.Attentions were focused on apparent morphology,phase transformation and thermal stability of the products of the P2O5＂absorption＂at different temperatures.The results show that the temperature significantly affected the＂absorption＂.The reaction between pure Ca3（PO4）2 and P2O5 occurred at 500℃.Calcium metaphosphate（Ca（PO3）2）was the primary product at the temperatures≤900℃ with its melting point≤900℃ while calcium pyrophosphate（Ca2P2O7）was obtained over 1000℃,which has a melting point≤1200℃.The＂absorption＂by pure SiO2 started at 800℃ and the most significant reaction occurred at 1000℃ with formation of silicon pyrophosphate（SiP2O7）product of melting point≤1000℃.Using mixed Ca3（PO4）2and SiO2as raw material,the＂absorption＂by Ca3（PO4）2 was enhanced due to existence of silica.At 600–700℃,silica was inert to P2O5and thus formed a porous structure in the raw material,which accelerated diffusion of gaseous P2O5inside the mixture.At higher temperatures,the combined＂absorption＂by calcium phosphate and reaction between silicon dioxide and the＂absorption＂product calcium pyrophosphate,reinforced the＂absorption＂by the mixture.Besides,it was found that both Ca（PO3）2and SiP2O7were unstable at high temperatures and would decompose to Ca2P2O7and SiO2,respectively,at over 1000℃ and 1100℃ with the release of gaseous P2O5at the same time.

Initial Stability Study of Calcium Phosphate Coated Dental Implants

Thin film of biodegradable calcium phosphate coated on threaded commercially pure titanium （ cp- Ti ） dental implants has been investigated as one of alternatives to eliminate the problem of the long- term instability of plasma sprayed HA coated implants. In order to compare in-vivo bone-to-implant response behavior among as-machined, HA coated and CMP coated groups, each group was implanted into New Zealand white mature male rabbits for 2 and 6 weeks, and then in-vivo biological behavior was examined in terms of H＆E staining. Initial stability and removable torques of implants were compared among three groups. Measured removable torque of CMP coated specimen at 6 weeks after inplantation was significantly higher than that of non-coated group, but slightly lower than that of HA coated group, without any inflammatory response at the surrounding of the implants. The initial stability （ ISQ value ; implant stability quotient ） of CMP coated specimen at 2 weeks after implantation was slightly lower than that of HA coated group and significantly higher than that of non-coated group. However, after 6 weeks, ISQ value of CMP coated group was slightly higher than that of HA coated group and significantly higher than that of non-coated group.

RESORBABLE HIGH-STRENGTH ROD FOR FRACTURE INTERNAL FIXATION

Objective To find an ideal biomaterial for internal fixation. Methods Forty rabbits with fracture of the femur diaphysis (superiorcondyle) were treated by intramedullary nailing of femur with composites rod of resorbable DL-polylactic acid (PDLLA)-calcium metaphosphate (CMP), while steinmann's pin as control. The fracture healing, the material degradation and its mechanical properties were studied by X-ray films, macroscopic, microscopic and electron microscopic observations. Results No significant inflammatory reaction was found, and all the osteotomies were healed, while material was resorbed. Conclusion The PDLLA-CMP has excellent biocompatibility and mechanical properties, and it can be a promising implant material in orthopaedics surgery.

Colloidal forming of macroporous calcium pyrophosphate bioceramics in 3D-printed molds

A technique for colloidal forming of Ca2P2O7 macroporous bioceramics,based on low-pressure injection molding(LPIM)of a glycerol-water slip containing Ca2P2O7 and Ca(Н2PO4)2 into a plastic mold fabricated via FDM 3Dprinting,was proposed.Chemical reaction between the solid phases of the water containing slip-Ca2P2O7 and Ca(Н2PO4)2,resulting in brushite(CaHPO4·2H2O)formation,led to consolidation of the casting and preserved its complex architecture in the course of mold burning-out.Macroporous ceramics of Kelvin structure(70%macropores with the sizes from 2 up to 4 mm),based on a pre-defined composition with 10 wt%Ca(PO3)2 and sintered in liquid-phase regime,demonstrated a compressive strength of 1.4±0.1 MPa at a density of 22±2%.In vitro tests on bioactivity in SBF solution,as well as on resorption of the ceramics in model solution of citric acid,were carried out.

Post-glass melting synthesis and photochromic properties of composite AgCl-AgPO_(3)glasses

We herein present a simple,fast,low-temperature,post-glass melting fabrication protocol in which a photochromic silver cation based modified zone is incorporated within silver metaphosphate glass(AgPO_(3)).The selection of AgPO_(3)glass is mainly based on its relative“soft”nature(T_(g)=192℃)that enables the integration of silver cations from the surface deposited AgCl layer,while being transparent in most of the visible range,and therefore suitable for smart photochromic window applications.The suggested synthesis procedure permits the controlled formation of a silver cation modified layer within the host glass matrix,while the characteristics of the layer itself can be adjusted correspondingly.Our findings reveal a direct relationship between the developed composite AgCleAgPO_(3)glass photochromic response and the morphological features of the integrated layer,i.e.,thickness and position.More importantly,the photochromic response time with various UV irradiation doses is also studied,where remarkable response times of several seconds are obtained.Processes and efforts to further enhance the photochromic performance by utilizing the presence of silver nanoparticles within the glass matrix are also presented and discussed.